Polymerization processes

ABSTRACT

The invention relates to new processes to produce polymers utilizing bayonette cooled slurry reactor systems and diluents including hydrofluorocarbons.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of Provisional Application Nos.60/435,061, filed Dec. 20, 2002, 60/464,187, filed Apr. 21, 2003, and60/479,081, filed Jun. 17, 2003, the disclosures of which areincorporated by reference.

FIELD OF INVENTION

The invention relates to new polymerization processes to producepolymers utilizing bayonette cooled reactor systems and diluentsincluding hydrofluorocarbons.

BACKGROUND

Isoolefin polymers are prepared in carbocationic polymerizationprocesses. Of special importance is butyl rubber which is a copolymer ofisobutylene with a small amount of isoprene. Butyl rubber is made by lowtemperature cationic polymerization that generally requires that theisobutylene have a purity of >99.5 wt % and the isoprene have a purityof >98.0 wt % to prepare high molecular weight butyl rubber.

The carbocationic polymerization of isobutylene and its copolymerizationwith comonomers like isoprene is mechanistically complex. See, e.g.,Organic Chemistry, SIXTH EDITION, Morrison and Boyd, Prentice-Hall,1084-1085, Englewood Cliffs, N.J. 1992, and K. Matyjaszewski, ed,Cationic Polymerizations, Marcel Dekker, Inc., New York, 1996. Thecatalyst system is typically composed of two components: an initiatorand a Lewis acid. Examples of Lewis acids include AlCl₃ and BF₃.Examples of initiators include Brønsted acids such as HCl, RCOOH(wherein R is an alkyl group), and H₂O. During the polymerizationprocess, in what is generally referred to as the initiation step,isobutylene reacts with the Lewis acid/initiator pair to produce acarbenium ion. Following, additional monomer units add to the formedcarbenium ion in what is generally called the propagation step. Thesesteps typically take place in a diluent or solvent. Temperature, diluentpolarity, and counterions affect the chemistry of propagation. Of these,the diluent is typically considered important.

Industry has generally accepted widespread use of a slurrypolymerization process (to produce butyl rubber, polyisobutylene, etc.)in the diluent methyl chloride. Typically, the polymerization processextensively uses methyl chloride at low temperatures, generally lowerthan −90° C., as the diluent for the reaction mixture. Methyl chlorideis employed for a variety of reasons, including that it dissolves themonomers and aluminum chloride catalyst but not the polymer product.Methyl chloride also has suitable freezing and boiling points to permit,respectively, low temperature polymerization and effective separationfrom the polymer and unreacted monomers. The slurry polymerizationprocess in methyl chloride offers a number of additional advantages inthat a polymer concentration of approximately 26% to 37% by volume inthe reaction mixture can be achieved, as opposed to the concentration ofonly about 8% to 12% in solution polymerization. An acceptablerelatively low viscosity of the polymerization mass is obtained enablingthe heat of polymerization to be removed more effectively by surfaceheat exchange. Slurry polymerization processes in methyl chloride areused in the production of high molecular weight polyisobutylene andisobutylene-isoprene butyl rubber polymers. Likewise polymerizations ofisobutylene and para-methylstyrene are also conducted using methylchloride. Similarly, star-branched butyl rubber is also produced usingmethyl chloride.

However, there are a number of problems associated with thepolymerization in methyl chloride, for example, the tendency of thepolymer particles in the reactor to agglomerate with each other and tocollect on the reactor wall, heat transfer surfaces, impeller(s), andthe agitator(s)/pump(s). The rate of agglomeration increases rapidly asreaction temperature rises. Agglomerated particles tend to adhere to andgrow and plate-out on all surfaces they contact, such as reactordischarge lines, as well as any heat transfer equipment being used toremove the exothermic heat of polymerization, which is critical sincelow temperature reaction conditions must be maintained.

The commercial reactors typically used to make these rubbers are wellmixed vessels of greater than 10 to 30 liters in volume with a highcirculation rate provided by a pump impeller. The polymerization and thepump both generate heat and, in order to keep the slurry cold, thereaction system needs to have the ability to remove the heat. An exampleof such a continuous flow stirred tank reactor (“CFSTR”) is found inU.S. Pat. No. 5,417,930, incorporated by reference, hereinafter referredto in general as a “reactor” or “butyl reactor”. In these reactors,slurry is circulated through tubes of a heat exchanger by a pump, whileboiling ethylene on the shell side provides cooling, the slurrytemperature being determined by the boiling ethylene temperature, therequired heat flux and the overall resistance to heat transfer. On theslurry side, the heat exchanger surfaces progressively accumulatepolymer, inhibiting heat transfer, which would tend to cause the slurrytemperature to rise. This often limits the practical slurryconcentration that can be used in most reactors from 26 to 37 volume %relative to the total volume of the slurry, diluent, and unreactedmonomers. The subject of polymer accumulation has been addressed inseveral patents (such as U.S. Pat. No. 2,534,698, U.S. Pat. No.2,548,415, U.S. Pat. No. 2,644,809). However, these patents haveunsatisfactorily addressed the myriad of problems associated withpolymer particle agglomeration for implementing a desired commercialprocess.

SU 1627243 A1, RU 2097122 C1, and RU 2209213 C1 disclose, inter alia,devices and slurry polymerization processes using diluents, when stated,such as methyl chloride, including reactors having tube bundles used forthe circulation of cooling media.

U.S. Pat. No. 2,534,698 discloses, inter alia, a polymerization processcomprising the steps in combination of dispersing a mixture ofisobutylene and a polyolefin having 4 to 14 carbon atoms per molecule,into a body of a fluorine substituted aliphatic hydrocarbon containingmaterial without substantial solution therein, in the proportion of fromone-half part to 10 parts of fluorine substituted aliphatic hydrocarbonhaving from one to five carbon atoms per molecule which is liquid at thepolymerization temperature and polymerizing the dispersed mixture ofisobutylene and polyolefin having four to fourteen carbon atoms permolecule at temperatures between −20° C. and −164° C. by the applicationthereto a Friedel-Crafts catalyst. However, '698 teaches that thesuitable fluorocarbons would result in a biphasic system with themonomer, comonomer and catalyst being substantially insoluble in thefluorocarbon making their use difficult and unsatisfactory.

U.S. Pat. No. 2,548,415 discloses, inter alia, a continuouspolymerization process for the preparation of a copolymer, the stepscomprising continuously delivering to a polymerization reactors a streamconsisting of a major proportion of isobutylene and a minor proportionisoprene; diluting the mixture with from ½ volume to 10 volumes ofethylidene difluoride; copolymerizing the mixture of isobutyleneisoprene by the continuous addition to the reaction mixture of a liquidstream of previously prepared polymerization catalyst consisting ofboron trifluoride in solution in ethylidene difluoride, maintaining thetemperature between −40° C. and −103° C. throughout the entirecopolymerization reaction. . . . '415 teaches the use of borontrifluoride and its complexes as the Lewis acid catalyst and1,1-difluoroethane as a preferred combination. This combination providesa system in which the catalyst, monomer and comonomer are all solubleand yet still affords a high degree of polymer insolubility to capturethe benefits of reduced reactor fouling. However, boron trifluoride isnot a preferred commercial catalyst for butyl polymers for a variety ofreasons.

U.S. Pat. No. 2,644,809 teaches, inter alia, a polymerization processcomprising the steps in combination of mixing together a majorproportion of a monoolefin having 4 to 8, inclusive, carbon atoms permolecule, with a minor proportion of a multiolefin having from 4 to 14,inclusive, carbon atoms per molecule, and polymerizing the resultingmixture with a dissolved Friedel-Crafts catalyst, in the presence offrom 1 to 10 volumes (computed upon the mixed olefins) of a liquidselected from the group consisting of dichlorodifluoromethane,dichloromethane, trichloromonofluormethane, dichloromonofluormethane,dichlorotetrafluorethane, and mixtures thereof, the monoolefin andmultiolefin being dissolved in said liquid, and carrying out thepolymerization at a temperature between −20° C and the freezing point ofthe liquid. '809 discloses the utility of chlorofluorocarbons atmaintaining ideal slurry characteristics and minimizing reactor fouling,but teaches the incorporation of diolefin (i.e. isoprene) by theaddition of chlorofluorocarbons (CFC). CFC's are known to beozone-depleting chemicals. Governmental regulations, however, tightlycontrols the manufacture and distribution of CFC's making thesematerials unattractive for commercial operation.

Additionally, Thaler, W. A, Buckley, Sr., D. J., High Molecular-Weight,High Unsaturation Copolymers of Isobutylene and Conjugated Dienes, 49(4)Rubber Chemical Technology, 960 (1976), discloses, inter alia, thecationic slurry polymerization of copolymers of isobutylene withisoprene (butyl rubber) and with cyclopentadiene in heptane.

Therefore, finding alternative diluents or blends of diluents to createnew polymerization systems that would reduce particle agglomerationand/or reduce the amount of chlorinated hydrocarbons such as methylchloride is desirable. Such new polymerization systems would reduceparticle agglomeration and reactor fouling without having to compromiseprocess parameters, conditions, or components and/or without sacrificingproductivity/throughput and/or the ability to produce high molecularweight polymers.

Hydrofluorocarbons (HFC's) are chemicals that are currently used asenvironmentally friendly refrigerants because they have a very low (evenzero) ozone depletion potential. Their low ozone depletion potential isthought to be related to the lack of chlorine. The HFC's also typicallyhave low flammability particularly as compared to hydrocarbons andchlorinated hydrocarbons.

Other background references include WO 02/34794 that discloses a freeradical polymerization process using hydrofluorocarbons. Otherbackground references include DE 100 61 727 A, WO 02/096964, WO00/04061, U.S. Pat. No. 5,624,878, U.S. Pat. No. 5,527,870, and U.S.Pat. No. 3,470,143.

SUMMARY OF THE INVENTION

The invention relates to new polymerization processes to producepolymers utilizing bayonette cooled slurry reactor systems and diluentscomprising hydrofluorocarbons. In particular, the invention provides fora process to produce polymers comprising contacting one or moremonomer(s), a catalyst system, and a diluent comprising one or morehydrofluorocarbon(s) (HFC's) in a reactor comprising a bayonette.

In any of the embodiments described in this section, the process may bea slurry polymerization process and the reactor may be a tubularreactor.

In any of the embodiments described in this section, the reactor mayfurther comprise a vertical cylindrical housing, an upper part, and alower part.

In any of the embodiments described in this section, the reactor mayfurther comprise connecting pipes for delivery of the catalyst system inthe lower part, and connecting pipes for the removal of the polymer inthe upper part.

In any of the embodiments described in this section, the reactor mayfurther comprise a shaft with blade mixers mounted along the height ofthe shaft.

In any of the embodiments described in this section, the bayonette maycomprise a plurality of tubes.

In the previous embodiment, the tubes may comprise sectors.

In any of the embodiments described in this section, the bayonette maycomprise tube disks and tube baffles.

In the previous embodiment, the tube baffles may comprise spaces betweenthe sectors.

In any of the previous embodiments, when present, the tube baffles maycomprise holes.

In the previous embodiments, the reactor may comprise a catalyst systemdelivery tube comprising an open end, the open end located in the spacebetween the tube baffles, when present.

In the previous embodiment, the open end of the catalyst system deliverytube is angled in a downward direction toward a mixer.

In any of the embodiments described in this section, the reactor maycomprise one or more catalyst system delivery tube(s) comprising openends.

In the previous embodiment, at least one open end is angled in adownward direction toward a mixer.

In any of the embodiments described in this section, the reactor maycomprises a mixer located adjacent to a tube baffle.

In any of the embodiments described in this section, the one or moremonomer(s) may comprise an isoolefin, preferably isobutylene, and amultiolefin, preferably a conjugated diene, more preferably isoprene.

In any of the embodiments described in this section, the one or moremonomer(s) may comprise an isoolefin, preferably isobutylene, and analkylstyrene, preferably methylstyrene, more preferablypara-methylstyrene.

In another aspect of the invention, the invention relates to apolymerization process comprising contacting one or more monomers, oneor more Lewis acids and one or more initiators in the presence of adiluent comprising one or more hydrofluorocarbons (HFC's) in a reactorunder polymerization conditions.

In another embodiment, this invention relates to a process to producepolymers of monomer(s) comprising contacting, in a reactor, themonomer(s) and a Lewis acid in the presence of a hydrofluorocarbondiluent, wherein the Lewis acid is not a compound represented by formulaMX₃, where M is a group 13 metal, X is a halogen.

In one embodiment, the invention provides a polymerization mediumsuitable to polymerize one or more monomer(s) to form a polymer, thepolymerization medium comprising one or more Lewis acid(s), one or moreinitiator(s), and a diluent comprising one or more hydrofluorocarbon(s)(HFC's).

In another embodiment, the invention provides a polymerization mediumsuitable to polymerize one or more monomer(s) to form a polymer, thepolymerization medium comprising one or more Lewis acid(s) and a diluentcomprising one or more hydrofluorocarbon(s) (HFC); wherein the one ormore Lewis acid(s) is not a compound represented by formula MX₃, where Mis a group 13 metal and X is a halogen.

In preferred embodiments, the polymerization processes and media asdescribed in any of the embodiments above produce polymers that include(poly)isobutylene homopolymers, isobutylene-isoprene (butyl rubber)copolymers, isobutylene and alkylstyrene copolymers, and star-branchedbutyl rubber terpolymers.

Bayonette cooled slurry reactor systems may be use in combination in anyof the aforementioned embodiments.

DRAWINGS

FIG. 1 is a graph of the relationship between dielectric constant andtemperature.

FIG. 2 is a drawing of diluent mass uptake as a function of volumefraction of hydrofluorocarbon in methyl chloride.

FIG. 3 is a plot of peak molecular weight (M_(p)) versus monomerconversion of certain inventive polymers as described herein.

FIG. 4 is an embodiment of a bayonette cooled slurry reactor system.

FIG. 5 is another embodiment of a bayonette cooled slurry reactorsystem.

FIG. 6 is yet another embodiment of a bayonette cooled slurry reactorsystem.

FIG. 7 is a horizontal cross section of the reactor shown in FIG. 6.

FIG. 8 is a horizontal cross section of a bundle of tubes of one of thebayonetters shown in FIG. 6 and FIG. 7.

DETAILED DESCRIPTION

Various specific embodiments, versions and examples of the inventionwill now be described, including preferred embodiments and definitionsthat are adopted herein for purposes of understanding the claimedinvention. For determining infringement, the scope of the “invention”will refer to any one or more of the appended claims, including theirequivalents, and elements or limitations that are equivalent to thosethat are recited.

For purposes of this invention and the claims thereto the term catalystsystem refers to and includes any Lewis acid(s) or other metalcomplex(es) (described herein) used to catalyze the polymerization ofthe olefinic monomers of the invention, as well as at least oneinitiator, and optionally other minor catalyst component(s).

In one embodiment, the invention provides a polymerization mediumsuitable to polymerize one or more monomer(s) to form a polymer, thepolymerization medium comprising one or more Lewis acid(s), one or moreinitiator(s), and a diluent comprising one or more hydrofluorocarbon(s)(HFC's). Optionally, the polymerization medium may include one or moremonomer(s).

In another embodiment, the invention provides a polymerization mediumsuitable to polymerize one or more monomer(s) to form a polymer, thepolymerization medium comprising one or more Lewis acid(s) and a diluentcomprising one or more hydrofluorocarbon(s) (HFC); wherein the one ormore Lewis acid(s) is not a compound represented by formula MX₃, where Mis a group 13 metal and X is a halogen. Optionally, the polymerizationmedium may include one or more monomer(s).

The phrase “suitable to polymerize monomers to form a polymer” relatesto the selection of polymerization conditions and components, wellwithin the ability of those skilled in the art necessary to obtain theproduction of a desired polymer in light of process parameters andcomponent properties described herein. There are numerous permutationsof the polymerization process and variations in the polymerizationcomponents available to produce the desired polymer attributes. Inpreferred embodiments, such polymers include polyisobutylenehomopolymers, isobutylene-isoprene (butyl rubber) copolymers,isobutylene and para-methylstyrene copolymers, and star-branched butylrubber terpolymers.

Diluent means a diluting or dissolving agent. Diluent is specificallydefined to include chemicals that can act as solvents for the LewisAcid, other metal complexes (as described herein), initiators, monomersor other additives. In the practice of the invention, the diluent doesnot alter the general nature of the components of the polymerizationmedium, i.e., the components of the catalyst system, monomers, etc.However, it is recognized that interactions between the diluent andreactants may occur. In preferred embodiments, the diluent does notreact with the catalyst system components, monomers, etc. to anyappreciable extent. Additionally, the term diluent includes mixtures ofat least two or more diluents.

A reactor is any container(s) in which a chemical reaction occurs.

A bayonette cooled reactor system is any system for the polymerizationof polymers comprising a tubular reactor comprising one or morebayonette(s) used for the circulation of a cooling medium such as arefrigerant(s). The bayonette may be a tube or a plurality or bundle oftubes.

Slurry refers to a volume of diluent comprising monomers that haveprecipitated from the diluent, monomers, Lewis acid, and initiator. Theslurry concentration is the volume percent of the partially orcompletely precipitated polymers based on the total volume of theslurry.

As used herein, the new numbering scheme for the Periodic Table Groupsare used as in CHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985).

Polymer may be used to refer to homopolymers, copolymers, interpolymers,terpolymers, etc. Likewise, a copolymer may refer to a polymercomprising at least two monomers, optionally with other monomers.

When a polymer is referred to as comprising a monomer, the monomer ispresent in the polymer in the polymerized form of the monomer or in thederivative form the monomer. Likewise, when catalyst components aredescribed as comprising neutral stable forms of the components, it iswell understood by one skilled in the art, that the ionic form of thecomponent is the form that reacts with the monomers to produce polymers.

Isoolefin refers to any olefin monomer having two substitutions on thesame carbon.

Multiolefin refers to any monomer having two double bonds.

Elastomer or elastomeric composition, as used herein, refers to anypolymer or composition of polymers consistent with the ASTM D1566definition. The terms may be used interchangeably with the term“rubber(s)”, as used herein.

Alkyl refers to a paraffinic hydrocarbon group which may be derived froman alkane by dropping one or more hydrogens from the formula, such as,for example, a methyl group (CH₃), or an ethyl group (CH₃CH₂), etc.

Aryl refers to a hydrocarbon group that forms a ring structurecharacteristic of aromatic compounds such as, for example, benzene,naphthalene, phenanthrene, anthracene, etc., and typically possessalternate double bonding (“unsaturation”) within its structure. An arylgroup is thus a group derived from an aromatic compound by dropping oneor more hydrogens from the formula such as, for example, phenyl, orC₆H₅.

Substituted refers to at least one hydrogen group by at least onesubstituent selected from, for example, halogen (chlorine, bromine,fluorine, or iodine), amino, nitro, sulfoxy (sulfonate or alkylsulfonate), thiol, alkylthiol, and hydroxy; alkyl, straight or branchedchain having 1 to 20 carbon atoms which includes methyl, ethyl, propyl,tert-butyl, isopropyl, isobutyl, etc.; alkoxy, straight or branchedchain alkoxy having 1 to 20 carbon atoms, and includes, for example,methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, secondarybutoxy, tertiary butoxy, pentyloxy, isopentyloxy, hexyloxy, heptryloxy,octyloxy, nonyloxy, and decyloxy; haloalkyl, which means straight orbranched chain alkyl having 1 to 20 carbon atoms which is substituted byat least one halogen, and includes, for example, chloromethyl,bromomethyl, fluoromethyl, iodomethyl, 2-chloroethyl, 2-bromoethyl,2-fluoroethyl, 3-chloropropyl, 3-bromopropyl, 3-fluoropropyl,4-chlorobutyl, 4-fluorobutyl, dichloromethyl, dibromomethyl,difluoromethyl, diiodomethyl, 2,2-dichloroethyl, 2,2-dibromomethyl,2,2-difluoroethyl, 3,3-dichloropropyl, 3,3-difluoropropyl,4,4-dichlorobutyl, 4,4-difluorobutyl, trichloromethyl,4,4-difluorobutyl, trichloromethyl, trifluoromethyl,2,2,2-trifluoroethyl, 2,3,3-trifluoropropyl, 1,1,2,2-tetrafluoroethyl,and 2,2,3,3-tetrafluoropropyl. Thus, for example, a “substitutedstyrenic unit” includes p-methylstyrene, p-ethylstyrene, etc.

In one embodiment, this invention relates to the use ofhydrofluorocarbon(s) or blends of hydrofluorocarbon(s) withhydrocarbon(s) and/or chlorinated hydrocarbon(s) to produce a polymerslurry which is less prone to fouling (i.e., also observed more glasslike, less sticky particles in the reaction vessel with reducedadherence to the walls of the vessel or to the stirring impeller as wellas reduced particle to particle agglomeration). More particularly, thisinvention relates to the use of hydrofluorocarbon diluent(s) or HFCdiluent blends with hydrocarbons and/or chlorinated hydrocarbon blendsto polymerize and copolymerize isoolefins with dienes and/oralkylstyrenes to produce isoolefin homopolymers and copolymers withsignificantly reduced reactor fouling. Further, this invention relatesto the use of hydrofluorocarbon diluent(s) or diluent blends withhydrocarbons and/or chlorinated hydrocarbon blends to polymerize andcopolymerize isoolefins with dienes to produce isoolefin copolymers withsignificantly reduced reactor fouling and hence longer run life for thereactors, as compared to conventional systems.

In another embodiment, the hydrofluorocarbons are used in a tubularreactor to obtain reduced polymer accumulation on the heat transfertubes and/or reduce polymer accumulation on the impeller and thus obtainlonger run life.

In another embodiment, the hydrofluorocarbons are used in a tubularreactor at higher temperatures to produce polymers at much greater runlengths (such as greater than 15 hours, preferably greater than 20hours, preferably greater than 30 hours, more preferably greater than 48hours than possible with other halogenated hydrocarbons.

In another preferred embodiment the hydrofluorocarbons are used in apolymerization process to obtain higher molecular weights at the sametemperature than when other halogenated hydrocarbons are used.

In one embodiment, this invention relates to the discovery of newpolymerization systems using diluents containing hydrofluorocarbons.These diluents effectively dissolve the selected catalyst system andmonomers but are relatively poor solvents for the polymer product.Polymerization systems using these diluents are less prone to foulingdue to the agglomeration of polymer particles to each other and theirdepositing on polymerization hardware. In addition, this inventionfurther relates to the use of these diluents in polymerization systemsfor the preparation of high molecular weight polymers and copolymers atequivalent to or higher than to those polymerization temperatures usingsolely chlorinated hydrocarbon diluents such as methyl chloride.

In another embodiment, this invention relates to the discovery of newpolymerization systems using fluorinated aliphatic hydrocarbons capableof dissolving the catalyst system. These polymerization systems are alsobeneficial for isoolefin slurry polymerization and production of apolymer slurry that is less prone to fouling, while permittingdissolution of monomer, comonomer and the commercially preferredalkylaluminum halide catalysts. In addition, this invention furtherrelates to the use of these diluents for the preparation of highmolecular weight polymers and copolymers at higher polymerizationtemperatures as compared to polymerization systems using solelychlorinated hydrocarbon diluents such as methyl chloride.

In yet another embodiment, this invention relates to the preparation ofisoolefinic homopolymers and copolymers, especially the polymerizationreactions required to produce the isobutylene-isoprene form of butylrubber and isobutylene-p-alkylstyrene copolymers. More particularly, theinvention relates to a method of polymerizing and copolymerizingisoolefins in a slurry polymerization process using hydrofluorocarbondiluents or blends of hydrofluorocarbons, and chlorinated hydrocarbondiluents, like methyl chloride.

In another embodiment, the polymerization systems of the presentinvention provide for copolymerizing an isomonoolefin having from 4 to 7carbon atoms and para-alkylstyrene monomers. In accordance with apreferred embodiment of the invention, the system produces copolymerscontaining between about 80 and 99.5 wt. % of the isoolefin such asisobutylene and between about 0.5 and 20 wt. % of the para-alkylstyrenesuch as para-methylstyrene. In accordance with another embodiment,however, where glassy or plastic materials are being produced as well,the copolymers are comprised between about 10 and 99.5 wt. % of theisoolefin, or isobutylene, and about 0.5 and 90 wt. % of thepara-alkylstyrene, such as para-methylstyrene.

In a preferred embodiment this invention relates to a process to producepolymers of cationically polymerizable monomer(s) comprising contacting,in a reactor, the monomer(s), a Lewis acid, and an initiator, in thepresence of an HFC diluent at a temperature of 0° C. or lower,preferably −10° C. or lower, preferably −20° C. or lower, preferably−30° C. or lower, preferably −40° C. or lower, preferably −50° C. orlower, preferably −60° C. or lower, preferably −70° C. or lower,preferably −80° C. or lower, preferably −90° C. or lower, preferably−100° C. or lower, preferably from 0° C. to the freezing point of thepolymerization medium, such as the diluent and monomer mixture.

Monomers and Polymers

Monomers which may be polymerized by this system include any hydrocarbonmonomer that is polymerizable using this invention. Preferred monomersinclude one or more of olefins, alpha-olefins, disubstituted olefins,isoolefins, conjugated dienes, non-conjugated dienes, styrenics and/orsubstituted styrenics and vinyl ethers. The styrenic may be substituted(on the ring) with an alkyl, aryl, halide or alkoxide group. Preferably,the monomer contains 2 to 20 carbon atoms, more preferably 2 to 9, evenmore preferably 3 to 9 carbon atoms. Examples of preferred olefinsinclude styrene, para-alkylstyrene, para-methylstyrene, alpha-methylstyrene, divinylbenzene, diisopropenylbenzene, isobutylene,2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-pentene, isoprene,butadiene, 2,3-dimethyl-1,3-butadiene, β-pinene, myrcene,6,6-dimethyl-fulvene, hexadiene, cyclopentadiene, piperylene, methylvinyl ether, ethyl vinyl ether, and isobutyl vinyl ether and the like.Monomer may also be combinations of two or more monomers. Styrenic blockcopolymers may also be used a monomers. Preferred block copolymersinclude copolymers of styrenics, such as styrene, para-methylstyrene,alpha-methylstyrene, and C₄ to C₃₀ diolefins, such as isoprene,butadiene, and the like. Particularly preferred monomer combinationsinclude 1) isobutylene and para-methyl styrene 2) isobutylene andisoprene, as well as homopolymers of isobutylene.

Additionally, preferred monomers include those that are cationicallypolymerizable as described in Cationic Polymerization of Olefins, ACritical Inventory, Joseph Kennedy, Wiley Interscience, New York 1975.Monomers include any monomer that is cationically polymerizable, such asthose monomers that are capable of stabilizing a cation or propagatingcenter because the monomer contains an electron donating group. For adetailed discussion of cationic catalysis please see CationicPolymerization of Olefins, A Critical Inventory, Joseph Kennedy, WileyInterscience, New York 1975.

The monomers may be present in the polymerization medium in an amountranging from 75 wt % to 0.01 wt % in one embodiment, alternatively 60 wt% to 0.1 wt %, alternatively from 40 wt % to 0.2 wt %, alternatively 30to 0.5 wt %, alternatively 20wt % to 0.8 wt %, alternatively and from 15wt % to 1 wt % in another embodiment.

Preferred polymers include homopolymers of any of the monomers listed inthis Section. Examples of homopolymers include polyisobutylene,polypara-methylstyrene, polyisoprene, polystyrene,polyalpha-methylstyrene, polyvinyl ethers (such as polymethylvinylether,polyethylvinylether).

Preferred polymers also include copolymers of 1) isobutylene and analkylstyrene; and 2) isobutylene and isoprene.

In one embodiment butyl polymers are prepared by reacting a comonomermixture, the mixture having at least (1) a C₄ to C₆ isoolefin monomercomponent such as isobutene with (2) a multiolefin, or conjugated dienemonomer component. The isoolefin is in a range from 70 to 99.5 wt % byweight of the total comonomer mixture in one embodiment, 85 to 99.5 wt %in another embodiment. In yet another embodiment the isoolefin is in therange of 92 to 99.5 wt %. The conjugated diene component in oneembodiment is present in the comonomer mixture from 30 to 0.5 wt % inone embodiment, and from 15 to 0.5 wt % in another embodiment. In yetanother embodiment, from 8 to 0.5 wt % of the comonomer mixture isconjugated diene. The C₄ to C₆ isoolefin may be one or more ofisobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, and4-methyl-1-pentene. The multiolefin may be a C₄ to C₁₄ conjugated dienesuch as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pinene,myrcene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene andpiperylene. One embodiment of the butyl rubber polymer of the inventionis obtained by reacting 85 to 99.5 wt % of isobutylene with 15 to 0.5 wt% isoprene, or by reacting 95 to 99.5 wt % isobutylene with 5.0 wt % to0.5 wt % isoprene in yet another embodiment. The following tableillustrates how the above-referenced wt % would be expressed as mol %.Wt % IC4^(a) mol % IC4 wt % IC5^(b) Mol % IC5 70 73.9 .5 .4 85 87.3 54.2 92 93.3 8 6.7 95 95.9 15 12.7 99.5 99.6 30 26.1^(a)IC4 - isobutylene^(b)IC5 - isoprene

This invention further relates to terpolymers and tetrapolymerscomprising any combination of the monomers listed above. Preferredterpolymers and tetrapolymers include polymers comprising isobutylene,isoprene and divinylbenzene, polymers comprising isobutylene,para-alkylstyrene (preferably paramethyl styrene) and isoprene, polymerscomprising cyclopentadiene, isobutylene, and paraalkyl styrene(preferably paramethyl styrene), polymers of isobutylene cyclopentadieneand isoprene, polymers comprising cyclopentadiene, isobutylene, andmethyl cyclopentadiene, polymers comprising isobutylene,paramethylstyrene and cyclopentadiene.

Lewis Acid

In a preferred embodiment the Lewis acid (also referred to as theco-initiator or catalyst) may be any Lewis acid based on metals fromGroup 4, 5, 13, 14 and 15 of the Periodic Table of the Elements,including boron, aluminum, gallium, indium, titanium, zirconium, tin,vanadium, arsenic, antimony, and bismuth. One skilled in the art willrecognize that some elements are better suited in the practice of theinvention. In one embodiment, the metals are aluminum, boron andtitanium, with aluminum being desirable. Illustrative examples includeAlCl₃, (alkyl)AlCl₂, (C₂H₅)₂AlCl and (C₂H₅)₃Al₂Cl₃, BF₃, SnCl₄, TiCl₄.In a particularly preferred embodiment, BF₃ is not the chosen Lewisacid.

The Group 4, 5 and 14 Lewis acids have the general formula MX₄; whereinM is Group 4, 5, or 14 metal; and X is a halogen independently selectedfrom the group consisting of fluorine, chlorine, bromine, and iodine,preferably chlorine. X may also be a psuedohalogen. For the purposes ofthis invention and the claims thereto pseudohalogen is defined to be anazide, an isocyanate, a thiocyanate, an isothiocyanate or a cyanide.Non-limiting examples include titanium tetrachloride, titaniumtetrabromide, vanadium tetrachloride, tin tetrachloride and zirconiumtetrachloride. The Group 4, 5, or 14 Lewis acids may also contain morethan one type of halogen. Non-limiting examples include titanium bromidetrichloride, titanium dibromide dichloride, vanadium bromidetrichloride, and tin chloride trifluoride.

Group 4, 5 and 14 Lewis acids useful in this invention may also have thegeneral formula MR_(n)X_(4-n); wherein M is Group 4, 5, or 14 metal;wherein R is a monovalent hydrocarbon radical selected from the groupconsisting of C₁ to C₁₂ alkyl, aryl, arylalkyl, alkylaryl and cycloalkylradicals; and n is an integer from 0 to 4; X is a halogen independentlyselected from the group consisting of fluorine, chlorine, bromine, andiodine, preferably chlorine. X may also be a psuedohalogen. For thepurposes of this invention and the claims thereto pseudohalogen isdefined to be an azide, an isocyanate, a thiocyanate, an isothiocyanateor a cyanide. The term “arylalkyl” refers to a radical containing bothaliphatic and aromatic structures, the radical being at an alkylposition. The term “alkylaryl” refers to a radical containing bothaliphatic and aromatic structures, the radical being at an arylposition. Non-limiting examples of these Lewis acids includebenzyltitanium trichloride, dibenzyltitanium dichloride, benzylzirconiumtrichloride, dibenzylzirconium dibromide, methyltitanium trichloride,dimethyltitanium difluoride, dimethyltin dichloride and phenylvanadiumtrichloride.

Group 4, 5 and 14 Lewis acids useful in this invention may also have thegeneral formula M(RO)_(n)R′_(m)X_(4-(m+n)); wherein M is Group 4, 5, or14 metal, wherein RO is a monovalent hydrocarboxy radical selected fromthe group consisting of C₁ to C₃₀ alkoxy, aryloxy, arylalkoxy,alkylaryloxy radicals; R′ is a monovalent hydrocarbon radical selectedfrom the group consisting of C₁ to C₁₂ alkyl, aryl, arylalkyl, alkylaryland cycloalkyl radicals as defined above; n is an integer from 0 to 4and m is an integer from 0 to 4 such that the sum of n and m is not morethan 4; X is a halogen independently selected from the group consistingof fluorine, chlorine, bromine, and iodine, preferably chlorine. X mayalso be a psuedohalogen. For the purposes of this invention and theclaims thereto pseudohalogen is defined to be an azide, an isocyanate, athiocyanate, an isothiocyanate or a cyanide. For the purposes of thisinvention, one skilled in the art would recognize that the terms alkoxyand aryloxy are structural equivalents to alkoxides and phenoxidesrespectively. The term “arylalkoxy” refers to a radical containing bothaliphatic and aromatic structures, the radical being at an alkoxyposition. The term “alkylaryl” refers to a radical containing bothaliphatic and aromatic structures, the radical being at an aryloxyposition. Non-limiting examples of these Lewis acids includemethoxytitanium trichloride, n-butoxytitanium trichloride,di(isopropoxy)titanium dichloride, phenoxytitanium tribromide,phenylmethoxyzirconium trifluoride, methyl methoxytitanium dichloride,methyl methoxytin dichloride and benzyl isopropoxyvanadium dichloride.

Group 4, 5 and 14 Lewis acids useful in this invention may also have thegeneral formula M(RC═OO)_(n)R′_(m)X_(4-(m+n)); wherein M is Group 4, 5,or 14 metal; wherein RC═OO is a monovalent hydrocarbacyl radicalselected from the group consisting of C₂ to C₃₀ alkacyloxy, arylacyloxy,arylalkylacyloxy, alkylarylacyloxy radicals; R′ is a monovalenthydrocarbon radical selected from the group consisting of C₁ to C₁₂alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals as definedabove; n is an integer from 0 to 4 and m is an integer from 0 to 4 suchthat the sum of n and m is not more than 4; X is a halogen independentlyselected from the group consisting of fluorine, chlorine, bromine, andiodine, preferably chlorine. X may also be a psuedohalogen. For thepurposes of this invention and the claims thereto pseudohalogen isdefined to be an azide, an isocyanate, a thiocyanate, an isothiocyanateor a cyanide. The term “arylalkylacyloxy” refers to a radical containingboth aliphatic and aromatic structures, the radical being at analkyacyloxy position. The term “alkylarylacyloxy” refers to a radicalcontaining both aliphatic and aromatic structures, the radical being atan arylacyloxy position. Non-limiting examples of these Lewis acidsinclude acetoxytitanium trichloride, benzoylzirconium tribromide,benzoyloxytitanium trifluoride, isopropoyloxytin trichloride, methylacetoxytitanium dichloride and benzyl benzoyloxyvanadium chloride.

Group 5 Lewis acids useful in this invention may also have the generalformula MOX₃; wherein M is a Group 5 metal; wherein X is a halogenindependently selected from the group consisting of fluorine, chlorine,bromine, and iodine, preferably chlorine. A non-limiting example isvanadium oxytrichloride.

The Group 13 Lewis acids useful in this invention have the generalformula MX₃; wherein M is a Group 13 metal and X is a halogenindependently selected from the group consisting of fluorine, chlorine,bromine, and iodine, preferably chlorine. X may also be a psuedohalogen.For the purposes of this invention and the claims thereto pseudohalogenis defined to be an azide, an isocyanate, a thiocyanate, anisothiocyanate or a cyanide. Non-limiting examples include aluminumtrichloride, boron trifluoride, gallium trichloride, and indiumtrifluoride.

Group 13 Lewis acids useful in this invention may also have the generalformula: MR_(n)X_(3-n), wherein M is a Group 13 metal; R is a monovalenthydrocarbon radical selected from the group consisting of C₁ to C₁₂alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals; and n is annumber from 0 to 3; X is a halogen independently selected from the groupconsisting of fluorine, chlorine, bromine, and iodine, preferablychlorine. X may also be a psuedohalogen. For the purposes of thisinvention and the claims thereto pseudohalogen is defined to be anazide, an isocyanate, a thiocyanate, an isothiocyanate or a cyanide. Theterm “arylalkyl” refers to a radical containing both aliphatic andaromatic structures, the radical being at an alkyl position. The term“alkylaryl” refers to a radical containing both aliphatic and aromaticstructures, the radical being at an aryl position. Non-limiting examplesof these Lewis acids include ethylaluminum dichloride, methylaluminumdichloride, benzylaluminum dichloride, isobutylgallium dichloride,diethylaluminum chloride, dimethylaluminum chloride, ethylaluminumsesquichloride, methylaluminum sesquichloride, trimethylaluminum andtriethylaluminum.

Group 13 Lewis acids useful in this invention may also have the generalformula M(RO)_(n)R′_(m)X_(3-(m+n)); wherein M is a Group 13 metal;wherein RO is a monovalent hydrocarboxy radical selected from the groupconsisting of C₁ to C₃₀ alkoxy, aryloxy, arylalkoxy, alkylaryloxyradicals; R′ is a monovalent hydrocarbon radical selected from the groupconsisting of C₁ to C₁₂ alkyl, aryl, arylalkyl, alkylaryl and cycloalkylradicals as defined above; n is a number from 0 to 3 and m is an numberfrom 0 to 3 such that the sum of n and m is not more than 3; X is ahalogen independently selected from the group consisting of fluorine,chlorine, bromine, and iodine, preferably chlorine. X may also be apsuedohalogen. For the purposes of this invention and the claims theretopseudohalogen is defined to be an azide, an isocyanate, a thiocyanate,an isothiocyanate or a cyanide. For the purposes of this invention, oneskilled in the art would recognize that the terms alkoxy and aryloxy arestructural equivalents to alkoxides and phenoxides respectively. Theterm “arylalkoxy” refers to a radical containing both aliphatic andaromatic structures, the radical being at an alkoxy position. The term“alkylaryl” refers to a radical containing both aliphatic and aromaticstructures, the radical being at an aryloxy position. Non-limitingexamples of these Lewis acids include methoxyaluminum dichloride,ethoxyaluminum dichloride, 2,6-di-tert-butylphenoxyaluminum dichloride,methoxy methylaluminum chloride, 2,6-di-tert-butylphenoxy methylaluminumchloride, isopropoxygallium dichloride and phenoxy methylindiumfluoride.

Group 13 Lewis acids useful in this invention may also have the generalformula M(RC═OO)_(n)R′_(m)X_(3-(m+n)); wherein M is a Group 13 metal;wherein RC═OO is a monovalent hydrocarbacyl radical selected from thegroup selected from the group consisting of C₂ to C₃₀ alkacyloxy,arylacyloxy, arylalkylacyloxy, alkylarylacyloxy radicals; R′ is amonovalent hydrocarbon radical selected from the group consisting of C₁to C₁₂ alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals asdefined above; n is a number from 0 to 3 and m is a number from 0 to 3such that the sum of n and m is not more than 3; X is a halogenindependently selected from the group consisting of fluorine, chlorine,bromine, and iodine, preferably chlorine. X may also be a psuedohalogen.For the purposes of this invention and the claims thereto pseudohalogenis defined to be an azide, an isocyanate, a thiocyanate, anisothiocyanate or a cyanide. The term “arylalkylacyloxy” refers to aradical containing both aliphatic and aromatic structures, the radicalbeing at an alkyacyloxy position. The term “alkylarylacyloxy” refers toa radical containing both aliphatic and aromatic structures, the radicalbeing at an arylacyloxy position. Non-limiting examples of these Lewisacids include acetoxyaluminum dichloride, benzoyloxyaluminum dibromide,benzoyloxygallium difluoride, methyl acetoxyaluminum chloride, andisopropoyloxyindium trichloride.

The Group 15 Lewis acids have the general formula MX_(y), wherein M is aGroup 15 metal and X is a halogen independently selected from the groupconsisting of fluorine, chlorine, bromine, and iodine, preferablychlorine and y is 3, 4 or 5. X may also be a psuedohalogen. For thepurposes of this invention and the claims thereto pseudohalogen isdefined to be an azide, an isocyanate, a thiocyanate, an isothiocyanateor a cyanide. Non-limiting examples include antimony hexachloride,antimony hexafluoride, and arsenic pentafluoride. The Group 15 Lewisacids may also contain more than one type of halogen. Non-limitingexamples include antimony chloride pentafluoride, arsenic trifluoride,bismuth trichloride and arsenic fluoride tetrachloride.

Group 15 Lewis acids useful in this invention may also have the generalformula MR_(n)X_(y-n); wherein M is a Group 15 metal; wherein R is amonovalent hydrocarbon radical selected from the group consisting of C₁to C₁₂ alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals; and nis an integer from 0 to 4; y is 3, 4 or 5 such that n is less than y; Xis a halogen independently selected from the group consisting offluorine, chlorine, bromine, and iodine, preferably chlorine. X may alsobe a pseudohalogen. For the purposes of this invention and the claimsthereto pseudohalogen is defined to be an azide, an isocyanate, athiocyanate, an isothiocyanate or a cyanide. The term “arylalkyl” refersto a radical containing both aliphatic and aromatic structures, theradical being at an alkyl position. The term “alkylaryl” refers to aradical containing both aliphatic and aromatic structures, the radicalbeing at an aryl position. Non-limiting examples of these Lewis acidsinclude tetraphenylantimony chloride and triphenylantimony dichloride.

Group 15 Lewis acids useful in this invention may also have the generalformula M(RO)_(n)R′_(m)X_(y-(m+n)); wherein M is a Group 15 metal,wherein RO is a monovalent hydrocarboxy radical selected from the groupconsisting of C₁ to C₃₀ alkoxy, aryloxy, arylalkoxy, alkylaryloxyradicals; R′ is a monovalent hydrocarbon radical selected from the groupconsisting of C₁ to C₁₂ alkyl, aryl, arylalkyl, alkylaryl and cycloalkylradicals as defined above; n is an integer from 0 to 4 and m is aninteger from 0 to 4 and y is 3, 4 or 5 such that the sum of n and m isless than y; X is a halogen independently selected from the groupconsisting of fluorine, chlorine, bromine, and iodine, preferablychlorine. X may also be a psuedohalogen. For the purposes of thisinvention and the claims thereto pseudohalogen is defined to be anazide, an isocyanate, a thiocyanate, an isothiocyanate or a cyanide. Forthe purposes of this invention, one skilled in the art would recognizethat the terms alkoxy and aryloxy are structural equivalents toalkoxides and phenoxides respectively. The term “arylalkoxy” refers to aradical containing both aliphatic and aromatic structures, the radicalbeing at an alkoxy position. The term “alkylaryl” refers to a radicalcontaining both aliphatic and aromatic structures, the radical being atan aryloxy position. Non-limiting examples of these Lewis acids includetetrachloromethoxyantimony, dimethoxytrichloroantimony,dichloromethoxyarsine, chlorodimethoxyarsine, and difluoromethoxyarsine.

Group 15 Lewis acids useful in this invention may also have the generalformula M(RC═OO)_(n)R′_(m)X_(y-(m+n)); wherein M is a Group 15 metal;wherein RC═OO is a monovalent hydrocarbacyloxy radical selected from thegroup consisting of C₂ to C₃₀ alkacyloxy, arylacyloxy, arylalkylacyloxy,alkylarylacyloxy radicals; R′ is a monovalent hydrocarbon radicalselected from the group consisting of C₁ to C₁₂ alkyl, aryl, arylalkyl,alkylaryl and cycloalkyl radicals as defined above; n is an integer from0 to 4 and m is an integer from 0 to 4 and y is 3, 4 or 5 such that thesum of n and m is less than y; X is a halogen independently selectedfrom the group consisting of fluorine, chlorine, bromine, and iodine,preferably chlorine. X may also be a psuedohalogen. For the purposes ofthis invention and the claims thereto pseudohalogen is defined to be anazide, an isocyanate, a thiocyanate, an isothiocyanate or a cyanide. Theterm “arylalkylacyloxy” refers to a radical containing both aliphaticand aromatic structures, the radical being at an alkyacyloxy position.The term “alkylarylacyloxy” refers to a radical containing bothaliphatic and aromatic structures, the radical being at an arylacyloxyposition. Non-limiting examples of these Lewis acids includeacetatotetrachloroantimony, (benzoato) tetrachloroantimony, and bismuthacetate chloride.

Particularly preferred Lewis acids may be any of those useful incationic polymerization of isobutylene copolymers including: aluminumtrichloride, aluminum tribromide, ethylaluminum dichloride,ethylaluminum sesquichloride, diethylaluminum chloride, methylaluminumdichloride, methylaluminum sesquichloride, dimethylaluminum chloride,boron trifluoride, titanium tetrachloride, etc. with ethylaluminumdichloride and ethylaluminum sesquichloride being preferred.

Lewis acids such as methylaluminoxane (MAO) and specifically designedweakly coordinating Lewis acids such as B(C₆F₅)₃ are also suitable Lewisacids within the context of the invention.

Initiator

Initiators useful in this invention are those initiators which arecapable of being complexed in a suitable diluent with the chosen Lewisacid to yield a complex which rapidly reacts with the olefin therebyforming a propagating polymer chain. Illustrative examples includeBrønsted acids such as H₂O, HCl, RCOOH (wherein R is an alkyl group),and alkyl halides, such as (CH₃)₃CCl, C₆H₅C(CH₃)₂Cl and(2-Chloro-2,4,4-trimethylpentane). More recently, transition metalcomplexes, such as metallocenes and other such materials that can act assingle site catalyst systems, such as when activated with weaklycoordinating Lewis acids or Lewis acid salts have been used to initiateisobutylene polymerization.

In one embodiment, the reactor and the catalyst system are substantiallyfree of water. Substantially free of water is defined as less than 30ppm (based upon total weight of the catalyst system), preferably lessthan 20 ppm, preferably less than 10 ppm, preferably less than 5 ppm,preferably less than 1 ppm. However, when water is selected as aninitiator, it is added to the catalyst system to be present at greaterthan 30 ppm, preferably greater than 40 ppm, and even more preferablygreater than 50 ppm (based upon total weight of the catalyst system).

In a preferred embodiment the initiator comprises one or more of ahydrogen halide, a carboxylic acid, a carboxylic acid halide, a sulfonicacid, an alcohol, a phenol, a tertiary alkyl halide, a tertiary aralkylhalide, a tertiary alkyl ester, a tertiary aralkyl ester, a tertiaryalkyl ether, a tertiary aralkyl ether, alkyl halide, aryl halide,alkylaryl halide, or arylalkylacid halide.

Preferred hydrogen halide initiators include hydrogen chloride, hydrogenbromide and hydrogen iodide. A particularly preferred hydrogen halide ishydrogen chloride.

Preferred carboxylic acids included both aliphatic and aromaticcarboxylic acids. Examples of carboxylic acids useful in this inventioninclude acetic acid, propanoic acid, butanoic acid; cinnamic acid,benzoic acid, 1-chloroacetic acid, dichloroacetic acid, trichloroaceticacid, trifluoroacetic acid, p-chlorobenzoic acid, and p-fluorobenzoicacid. Particularly preferred carboxylic acids include trichloroaceticacid, trifluoroacteic acid, and p-fluorobenzoic acid.

Carboxylic acid halides useful in this invention are similar instructure to carboxylic acids with the substitution of a halide for theOH of the acid. The halide may be fluoride, chloride, bromide, oriodide, with the chloride being preferred. Preparation of acid halidesfrom the parent carboxylic acids are known in the prior art and oneskilled in the art should be familiar with these procedures. Carboxylicacid halides useful in this invention include acetyl chloride, acetylbromide, cinnamyl chloride, benzoyl chloride, benzoyl bromide,tichloroacetyl chloride, trifluoroacetylchloride, trifluoroacetylchloride and p-fluorobenzoylchloride. Particularly preferred acidhalides include acetyl chloride, acetyl bromide, trichloroacetylchloride, trifluoroacetyl chloride and p-fluorobenzoyl chloride.

Sulfonic acids useful as initiators in this invention include bothaliphatic and aromatic sulfonic acids. Examples of preferred sulfonicacids include methanesulfonic acid, trifluoromethanesulfonic acid,trichloromethanesulfonic acid and p-toluenesulfonic acid.

Sulfonic acid halides useful in this invention are similar in structureto sulfonic acids with the substitution of a halide for the OH of theparent acid. The halide may be fluoride, chloride, bromide or iodide,with the chloride being preferred. Preparation of the sulfonic acidhalides from the parent sulfonic acids are known in the prior art andone skilled in the art should be familiar with these procedures.Preferred sulfonic acid halides useful in this invention includemethanesulfonyl chloride, methanesulfonyl bromide,trichloromethanesulfonyl chloride, trifluoromethanesulfonyl chloride andp-toluenesulfonyl chloride.

Alcohols useful in this invention include methanol, ethanol, propanol,2-propanol, 2-methylpropan-2-ol, cyclohexanol, and benzyl alcohol.Phenols useful in this invention include phenol; 2-methylphenol;2,6-dimethylphenol; p-chlorophenol; p-fluorophenol;2,3,4,5,6-pentafluorophenol; and 2-hydroxynaphthalene.

Preferred tertiary alkyl and aralkyl initiators include tertiarycompounds represented by the formula below:

wherein X is a halogen, pseudohalogen, ether, or ester, or a mixturethereof, preferably a halogen, preferably chloride and R₁, R₂ and R₃ areindependently any linear, cyclic or branched chain alkyls, aryls orarylalkyls, preferably containing 1 to 15 carbon atoms and morepreferably 1 to 8 carbon atoms. n is the number of initiator sites andis a number greater than or equal to 1, preferably between 1 to 30, morepreferably n is a number from 1 to 6. The arylalkyls may be substitutedor unsubstituted. For the purposes of this invention and any claimsthereto, arylalkyl is defined to mean a compound containing botharomatic and aliphatic structures. Preferred examples of initiatorsinclude 2-chloro-2,4,4-trimethylpentane; 2-bromo-2,4,4-trimethylpentane;2-chloro-2-methylpropane; 2-bromo-2-methylpropane;2-chloro-2,4,4,6,6-pentamethylheptane;2-bromo-2,4,4,6,6-pentamethylheptane; 1-chloro-1-methylethylbenzene;1-chloroadamantane; 1-chloroethylbenzene;1,4-bis(1-chloro-1-methylethyl)benzene;5-tert-butyl-1,3-bis(1-chloro-1-methylethyl)benzene;2-acetoxy-2,4,4-trimethylpentane; 2-benzoyloxy-2,4,4-trimethylpentane;2-acetoxy-2-methylpropane; 2-benzoyloxy-2-methylpropane;2-acetoxy-2,4,4,6,6-pentamethylheptane;2-benzoyl-2,4,4,6,6-pentamethylheptane; 1-acetoxy-1-methylethylbenzene;1-aceotxyadamantane; 1-benzoyloxyethylbenzene;1,4-bis(1-acetoxy-1-methylethyl)benzene;5-tert-butyl-1,3-bis(1-acetoxy-1-methylethyl)benzene;2-methoxy-2,4,4-trimethylpentane; 2-isopropoxy-2,4,4-trimethylpentane;2-methoxy-2-methylpropane; 2-benzyloxy-2-methylpropane;2-methoxy-2,4,4,6,6-pentamethylheptane;2-isopropoxy-2,4,4,6,6-pentamethylheptane;1-methoxy-1-methylethylbenzene; 1-methoxyadamantane;1-methoxyethylbenzene; 1,4-bis(1-methoxy-1-methylethyl)benzene;5-tert-butyl-1,3-bis(1-methoxy-1-methylethyl)benzene and1,3,5-tris(1-chloro-1-methylethyl)benzene. Other suitable initiators canbe found in U.S. Pat. No. 4,946,899, which is herein incorporated byreference. For the purposes of this invention and the claims theretopseudohalogen is defined to be any compound that is an azide, anisocyanate, a thiocyanate, an isothiocyanate or a cyanide.

Another preferred initiator is a polymeric halide, one of R₁, R₂ or R₃is an olefin polymer and the remaining R groups are defined as above.Preferred olefin polymers include polyisobutylene, polypropylene, andpolyvinylchloride. The polymeric initiator may have halogenated tertiarycarbon positioned at the chain end or along or within the backbone ofthe polymer. When the olefin polymer has multiple halogen atoms attertiary carbons, either pendant to or within the polymer backbone, theproduct may contain polymers which have a comb like structure and/orside chain branching depending on the number and placement of thehalogen atoms in the olefin polymer. Likewise, the use of a chain endtertiary polymer halide initiator provides a method for producing aproduct which may contain block copolymers.

Particularly preferred initiators may be any of those useful in cationicpolymerization of isobutylene copolymers including: hydrogen chloride,2-chloro-2,4,4-trimethylpentane, 2-chloro-2-methylpropane,1-chloro-1-methylethylbenzene, and methanol.

Catalyst system compositions useful in this invention typically comprise(1) an initiator and (2) a Lewis acid coinitiator, or other metalcomplex(es) herein described. In a preferred embodiment, the Lewis acidcoinitiator is present anywhere from about 0.1 moles times the moles ofinitiator present to about 200 times the moles of initiator present. Ina further preferred embodiment, the Lewis acid coinitiator is present atanywhere from about 0.8 times the moles of initiator present to about 20times the moles of initiator present. In a preferred embodiment theinitiator is present at anywhere from about 0.1 moles per liter to about10⁻⁶ moles per liter. It is of course understood that greater or lesseramounts of initiator are still within the scope of this invention.

The amount of the catalyst employed will depend on desired molecularweight and molecular weight distribution of the polymer being produced.Typically the range will be from about 1×10⁻⁶ moles per liter to 3×10⁻²moles per liter and most preferably from 10⁻⁴ to 10⁻³ moles per liter.

Catalyst systems useful in this invention may further comprise acatalyst composition comprising of a reactive cation and aweakly-coordinating anion (“WC anion” or “WCA” or “NCA”). The catalystcomposition comprising the WC anion will include a reactive cation andin certain instances are novel catalyst systems.

A weakly-coordinating anion is defined as an anion which either does notcoordinate to the cation or which is weakly coordinated to the cationand when the anion is functioning as the stabilizing anion in thisinvention the WCA does not transfer an anionic fragment or substituentto the cation thus creating a neutral by-product or other neutralcompound. Preferred examples of such weakly-coordinating anions include:alkyltris(pentafluorophenyl)boron (RB(pfp)₃ ⁻),tetraperfluorophenylboron (B(pfp)₄ ⁻), tetraperfluorophenylaluminumcarboranes, halogenated carboranes and the like. The cation is anycation that can add to an olefin to create a carbocation.

The anion may be combined with the cation by any method known to thoseof ordinary skill in the art. For example in a preferred embodiment theWC anion is introduced into the diluent as a compound containing boththe anion and the cation in the form of the active catalyst system. Inanother preferred embodiment a composition containing the WC anionfragment is first treated to produce the anion in the presence of thecation or reactive cation source, i.e. the anion is activated. Likewisethe WC anion may be activated without the presence of the cation orcation source which is subsequently introduced. In a preferredembodiment a composition containing the anion and a compositioncontaining the cation are combined and allowed to react to form aby-product, the anion and the cation.

Weakly-Coordinating Anions

Any metal or metalloid compound capable of forming an anionic complexwhich is incapable of transferring a substituent or fragment to thecation to neutralize the cation to produce a neutral molecule may beused as the WC anion. In addition any metal or metalloid capable offorming a coordination complex which is stable in water may also be usedor contained in a composition comprising the anion. Suitable metalsinclude, but are not limited to aluminum, gold, platinum and the like.Suitable metalloids include, but are not limited to, boron, phosphorus,silicon and the like. Compounds containing anions which comprisecoordination complexes containing a single metal or metalloid atom are,of course, well known and many, particularly such compounds containing asingle boron atom in the anion portion, are available commercially. Inlight of this, salts containing anions comprising a coordination complexcontaining a single boron atom are preferred.

In general, WC anions may be represented by the following generalformula:[(M′)^(m+)Q₁ . . . Q_(n)]^(d−)wherein:

M′ is a metal or metalloid;

Q₁ to Q_(n) are, independently, bridged or unbridged hydride radicals,dialkylamido radicals, alkoxide and aryloxide radicals, hydrocarbyl andsubstituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbylradicals and hydrocarbyl and halocarbyl-substituted organometalloidradicals and any one, but not more than one of Q₁ to Q_(n) may be ahalide radical;

m is an integer representing the formal valence charge of M;

n is the total number of ligands q, and

d is an integer greater than or equal to 1.

It is of course understood that the anions described above and below maybe counter balanced with a positively charged component that is removedbefore the anion acts with the cation. The same is true for cationsdescribed for use with the anions. For example, Cp₂ZrMe₂ may be combinedwith a composition comprising the anion (WCA⁻R⁺) where R⁺ acts with a Megroup to leave the Cp₂Zr⁺Me WCA⁻ catalyst system.

Preferred WC anions comprising boron may be represented by the followinggeneral formula:[BAr₁Ar₂X₃X₄]⁻wherein:

B is a boron in a valence state of 3;

Ar₁ and Ar₂ are the same or different aromatic or substituted-aromatichydrocarbon radicals containing from about 6 to about 20 carbon atomsand may be linked to each other through a stable bridging group; and

X₃ and X₄ are, independently, hydride radicals, hydrocarbyl andsubstituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbylradicals, hydrocarbyl- and halocarbyl-substituted organometalloidradicals, disubstituted pnictogen radicals, substituted chalcogenradicals and halide radicals, with the proviso that X₃ and X₄ will notbe halide at the same time.

In general, Ar₁ and Ar₂ may, independently, be any aromatic ofsubstituted-aromatic hydrocarbon radical. Suitable aromatic radicalsinclude, but are not limited to, phenyl, naphthyl and anthracenylradicals. Suitable substituents on the substituted-aromatic hydrocarbonradicals, include, but are not necessarily limited to, hydrocarbylradicals, organometalloid radicals, alkoxy and aryloxy radicals,fluorocarbyl and fluorohydrocarbyl radicals and the like such as thoseuseful as X₃ and X₄. The substituent may be ortho, meta or para,relative to the carbon atoms bonded to the boron atom. When either orboth X₃ and X₄ are a hydrocarbyl radical, each may be the same or adifferent aromatic or substituted-aromatic radical as are Ar₁ and Ar₂,or the same may be a straight or branched alkyl, alkenyl or alkynylradical, a cyclic hydrocarbon radical or an alkyl-substituted cyclichydrocarbon radical. As indicated above, Ar₁ and Ar₂ could be linked toeither X₃ or X₄. Finally, X₃ and X₄ may also be linked to each otherthrough a suitable bridging group.

Illustrative, but not limiting, examples of boron components which maybe used as WC anions are: tetravalent boron compounds such astetra(phenyl)boron, tetra(p-tolyl)boron, tetra(o-tolyl)boron,tetra(pentafluorophenyl)boron, tetra(o,p-dimethylphenyl)boron,tetra(m,m-dimethylphenyl)boron, (p-tri-fluoromethylphenyl)boron and thelike.

Similar lists of suitable components containing other metals andmetalloids which are useful as WC anions may be made, but such lists arenot deemed necessary to a complete disclosure. In this regard, it shouldbe noted that the foregoing list is not intended to be exhaustive andthat other useful boron compounds as well as useful compounds containingother metals or metalloids would be readily apparent to those skilled inthe art from the foregoing general discussion and formulae.

A particularly preferred WC anion comprising boron may be represented bythe following general formula:[B(C₆F₅)₃Q]⁻wherein:

F is fluorine, C is carbon and B, and Q are as defined above.Illustrative but not limiting, examples of these preferred WC anionscomprising boron triphenylmethyl salts where Q is a simple hydrocarbylsuch as methyl, butyl, cyclohexyl, or phenyl or where Q is a polymerichydrocarbyl of indefinite chain length such as polystyrene,polyisoprene, or poly-paramethylstyrene.

Polymeric Q substituents on the most preferred anion offer the advantageof providing a highly soluble ion-exchange activator component and finalcatalyst. Soluble catalysts and/or precursors are often preferred overinsoluble waxes, oils, or solids because they can be diluted to adesired concentration and can be transferred easily using simpleequipment in commercial processes.

WC anions containing a plurality of boron atoms may be represented bythe following general formulae:[(CX)_(a)(BX′)_(m)X″_(b)]^(c−)or[[[(CX₆)_(a)(BX₇)_(m)(X₈)_(b)]^(c−)]₂T^(n+)]^(d−)wherein:

X, X′, X″, X₆, X₇ and X₈ are, independently, hydride radicals, halideradicals, hydrocarbyl radicals, substituted-hydrocarbyl radicals,halocarbyl radicals, substituted-halocarbyl radicals, or hydrocarbyl- orhalocarbyl-substituted organometalloid radicals;

T is a transition metal, preferably a group 8, 9, or 10 metal,preferably nickel, cobalt or iron;

a and b are integers ≧0;

c is an integer ≧1;

a+b+c=an even-numbered integer from 2 to about 8;

m is an integer ranging from 5 to about 22;

a and b are the same or a different integer 0;

c is an integer ≧2;

a+b+c=an even-numbered integer from 4 to about 8;

m is an integer from 6 to about 12;

n is an integer such that 2c−n=d; and

d is an integer ≧1.

Examples of preferred WC anions of this invention comprising a pluralityof boron atoms include:

(1) A borane or carborane anion satisfying the general formula:[(CH)_(ax)(BH)_(bx)]^(cx−)wherein:

ax is either 0 or 1;

cx is either 1 or 2;

ax+cx=2;

bx is an integer ranging from about 10 to 12; or

(2) A borane or carborane or a neutral borane or carborane compoundsatisfying the general formula:[(CH)_(ay)(BH)_(my)(H)_(by)]^(cy−)wherein:

ay is an integer from 0 to 2;

by is an integer from 0 to 3;

cy is an integer from 0 to 3;

ay+by+cy=4;

my is an integer from about 9 to about 18; or

(3) A metallaborane or metallacarborane anion satisfying the followinggeneral formula:[[[(CH)_(az)(BH)_(mz)(H)_(bz)]^(cz−)]₂M^(nz+)]^(dz−)wherein:

az is an integer from 0 to 2;

bz is an integer from 0 to 2;

cz is either 2 or 3;

mz is an integer from about 9 to 11;

az+bz+cz=4; and

nz and dz are, respectively, 2 and 2 or 3 and 1.

Illustrative, but not limiting, examples of WC anions include:

carboranes such as dodecaborate, decachlorodecaborate,dodecachlorododecaborate, 1-carbadecaborate, 1-carbadecaborate,1-trimethylsilyl-1-carbadecaborate;

Borane and carborane complexes and salts of borane and carborane anionssuch as decaborane(14), 7,8-dicarbadecaborane(13),2,7-dicarbaundecaborane(13),undecahydrido-7,8-dimethyl-7,8-dicarbaundecaborane,6-carbadecaborate(12), 7-carbaundecaborate, 7,8-dicarbaudecaborate; and

Metallaborane anions such asbis(nonahydrido-1,3-dicarbanonaborato)cobaltate(III),bis(undecahydrido-7,8-dicarbaundecaborato)ferrate(III),bis(undecahydrido-7,8-dicarbaundecaborato)cobaltate(III),bis(undecahydrido-7,8-dicarbaunaborato)nickelate(III),bis(nonahydrido-7,8-dimethyl-7,8-dicarbaundecaborato)ferrate(III),bis(tribromooctahydrido-7,8-dicarbaundecaborato)cobaltate(III),bis(undecahydridodicarbadodecaborato)cobaltate(III) andbis(undecahydrido-7-carbaundecaborato)cobaltate(III).

The WC anion compositions most preferred for forming the catalyst systemused in this process are those containing a trisperfluorophenyl boron,tetrapentafluorphenyl boron anion and/or two or moretrispentafluorophenyl boron anion groups covalently bond to a centralatomic molecular or polymeric complex or particle.

Cationic Component

In various preferred embodiments of this invention the WC anion iscombined with one or more cations that are selected from differentclasses of cations and cation sources.

Some preferred classes are:

-   -   (A) cyclopentadienyl transition metal complexes and derivatives        thereof    -   (B) a substituted carbocation whose composition is represented        by the formula:        wherein R₁, R₂ and R₃ are hydrogen, alkyl, aryl, aralkyl groups        or derivatives thereof, preferably C₁ to C₃₀ alkyl, aryl,        aralkyl groups or derivatives thereof;    -   (C) substituted silylium; preferably those represented by the        formula:        wherein R₁, R₂ and R₃ are hydrogen, alkyl, aryl, aralkyl groups        or derivatives thereof, preferably C₁ to C₃₀ alkyl, aryl,        aralkyl groups or derivatives thereof;    -   (D) compositions capable of generating a proton; and    -   (E) cationic compositions of germanium, tin or lead, some of        which are represented by the formula:        wherein R₁, R₂ and R₃ are hydrogen, alkyl, aryl, aralkyl groups        or derivatives thereof, preferably C₁ to C₃₀ alkyl, aryl,        aralkyl groups or derivatives thereof, and R* is Ge, Sn or Pb.        A. Cyclopentadienyl Metal Derivatives

Preferred cyclopentadienyl transition metal derivatives includetransition metals that are a mono-, bis- or tris-cyclopentadienylderivative of a group 4, 5 or 6 transition metal, preferably amono-cyclopentadienyl (Mono-Cp) or bis-cyclopentadienyl (Bis-Cp) group 4transition metal compositions, particularly a zirconium, titanium orhafnium compositions.

Preferred cyclopentadienyl derivatives (cation sources) that may becombined with weakly-coordinating anions are represented by thefollowing formulae:

wherein:

(A-Cp) is either (Cp)(Cp*) or Cp-A′-Cp*;

Cp and Cp* are the same or different cyclopentadienyl rings substitutedwith from zero to five substituent groups S, each substituent group Sbeing, independently, a radical group which is a hydrocarbyl,substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl,hydrocarbyl-substituted organometalloid, halocarbyl-substitutedorganometalloid, disubstituted boron, disubstituted pnictogen,substituted chalcogen or halogen radicals, or Cp and Cp* arecyclopentadienyl rings in which any two adjacent S groups are joinedforming a C₄ to C₂₀ ring to give a saturated or unsaturated polycycliccyclopentadienyl ligand;

R is a substituent on one of the cyclopentadienyl radicals which is alsobonded to the metal atom;

A′ is a bridging group, which group may serve to restrict rotation ofthe Cp and Cp* rings or (C₅H_(5-y-x)S_(x)) and JR′_((z-1-y)) groups;

M is a group 4, 5, or 6 transition metal;

y is 0 or 1;

(C₅H_(5-y-x)S_(x)) is a cyclopentadienyl ring substituted with from zeroto five S radicals;

x is from 0 to 5 denoting the degree of substitution;

JR′_((z-1-y)) is a heteroatom ligand in which J is a group 15 elementwith a coordination number of three or a group 16 element with acoordination number of 2, preferably nitrogen, phosphorus, oxygen orsulfur;

R″ is a hydrocarbyl group, preferably an alkyl group;

X and X₁ are independently a hydride radical, hydrocarbyl radical,substituted hydrocarbyl radical, halocarbyl radical, substitutedhalocarbyl radical, and hydrocarbyl- and halocarbyl-substitutedorganometalloid radical, substituted pnictogen radical, or substitutedchalcogen radicals; and

L is an olefin, diolefin or aryne ligand, or a neutral Lewis base.

Additional cyclopentadienyl compounds that may be used in this inventionare described in U.S. Pat. Nos. 5,055,438, 5,278,119, 5,198,401 and5,096,867, which are incorporated by reference herein.

B. Substituted Carbocations

Another preferred source for the cation is substituted carbocations.Preferred examples include substances that are represented by theformula:

wherein R₁, R₂ and R₃ are independently hydrogen, or a linear, branchedor cyclic aromatic or aliphatic groups, preferably a C₁ to C₂₀ aromaticor aliphatics group, provided that only one of R₁, R₂ or R₃ may behydrogen. In a preferred embodiment none of R₁, R₂ or R₃ are H.Preferred aromatics include phenyl, toluyl, xylyl, biphenyl and thelike. Preferred aliphatics include methyl, ethyl, propyl, butyl, pentyl,hexyl, octyl, nonyl, decyl, dodecyl, 3-methylpentyl,3,5,5-trimethylhexyl and the like. In a particularly preferredembodiment, when R₁, R₂ and R₃ are phenyl groups, the addition of analiphatic or aromatic alcohol significantly enhances the polymerizationof isobutylene.C. Substituted Silylium Cations

In another preferred embodiment, substituted silylium compositions,preferably trisubstituted silylium compositions are combined with WCA'sto polymerize monomers. Preferred silylium cations are those representedby the formula:

wherein R₁, R₇ and R₃, are independently hydrogen, or a linear, branchedor cyclic aromatic or aliphatic group, with the proviso that only one ofR₁, R₂ and R₃ may be hydrogen. Preferably, none of R₁, R₂ and R₃ are H.Preferably, R₁ R₂ and R₃ are, independently, a C₁ to C₂₀ aromatic oraliphatic group. More preferably, R₁, R₂ and R₃ are independently a C₁to C₈ alkyl group. Examples of useful aromatic groups may be selectedfrom the group consisting of phenyl, tolyl, xylyl and biphenyl.Non-limiting examples of useful aliphatic groups may be selected fromthe group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl,octyl, nonyl, decyl, dodecyl, 3-methylpentyl and 3,5,5-trimethylhexyl. Aparticularly preferred group of reactive substituted silylium cationsmay be selected from the group consisting of trimethylsilylium,triethylsilylium and benzyldimethylsilylium.

For a discussion of stable forms of the substituted silylium andsynthesis thereof, see F. A. Cotton, G. Wilkinson, Advanced InorganicChemistry, John Wiley and Sons, New York 1980. Likewise for stable formsof the cationic tin, germanium and lead compositions and synthesisthereof, see Dictionary of Organometallic compounds, Chapman and HallNew York 1984.

D. Composition Capable of Generating a Proton

A fourth source for the cation is any compound that will produce aproton when combined with the weakly-coordinating anion or a compositioncontaining a weakly-coordinating anion. Protons may be generated fromthe reaction of a stable carbocation salt which contains aweakly-coordinating, non-nucleophilic anion with water, alcohol orphenol present to produce the proton and the corresponding by-product,(ether in the case of an alcohol or phenol and alcohol in the case ofwater). Such reaction may be preferred in the event that the reaction ofthe carbocation salt is faster with the protonated additive as comparedwith its reaction with the olefin. Other proton generating reactantsinclude thiols, carboxylic acids, and the like. Similar chemistries maybe realized with silylium type catalysts. In a particularly preferredembodiment, when R₁, R₂ and R₃ are phenyl groups, the addition of analiphatic or aromatic alcohol significantly enhances the polymerizationof isobutylene.

Another method to generate a proton comprises combining a group 1 orgroup 2 metal, preferably lithium, with water, such as by means of in awet diluent, in the presence of a Lewis base that does not interferewith polymerization, such as an olefin. It has been observed that when aLewis base, such as isobutylene, is present with the group 1 or 2 metaland the water, a proton is generated. In a preferred embodiment theweakly-coordinating anion is also present in the “wet” diluent such thatactive catalyst is generated when the group 1 or 2 metal is added.

Active Catalyst System

A. Cyclopentadienyl Transition Metal Compounds

The Cp transition metal cations (CpTm⁺) can be combined into an activecatalyst in at least two ways. A first method is to combine a compoundcomprising the CpTm⁺ with a second compound comprising the WCA⁻ whichthen react to form by-product and the active “weakly-coordinating” pair.Likewise, the CpTm⁺ compound may also be directly combined with the WCA⁻to form the active catalyst system. Typically the WCA is combined withthe cation/cation source in ratios of 1 to 1, however ratios of 100 to 1(CpTm⁺ to WCA) also work in the practice of this invention.

Active cationic catalysts can be prepared by reacting a transition metalcompound with some neutral Lewis acids, such as B(C₆F₆)_(3n), which uponreaction with a hydrolyzable ligand (X) of the transition metal compoundforms an anion, such as ([B(C₆F₅)₃(X)]⁻), which stabilizes the cationictransition metal species generated by the reaction.

A novel aspect of this invention is the active carbocationic catalystcomplex which is formed and which can be represented by the formulae:

wherein each G is independently hydrogen or an aromatic or aliphaticgroup, preferably a C₁ to C₁₀₀ aliphatic group, and g is an integerrepresenting the number of monomer units incorporated into the growingpolymer chain, g is preferably a number greater than or equal to 1,preferably a number from 1 to about 150,000. WCA⁻ is anyweakly-coordinating anion as described above. All other symbols are asdefined above.

In another embodiment this invention also provides active catalystcompositions which can be represented by the formulae:

wherein each G is independently a aliphatic or aromatic group,preferably a C₁ to C₁₀₀ aliphatic or aromatic group, and g is a ninteger representing the number of monomer units incorporated into thegrowing polymer chain, g is preferably a number greater than or equal to1, preferably a number from 1 to about 50,000. WCA⁻ is anyweakly-coordinating anion as described above. All other symbols are asdefined above.B. Substituted Carbocation and Silylium Compounds

Generation of trisubstituted carbocations and silylium cations may beperformed before use in the polymerization or in situ. Pre-formation andisolation of the cation or the stable cation salts may be accomplishedby reacting the alkali or alkaline earth metal salt of theweakly-coordinating anion with the corresponding halogen of thepotential carbocation or silylium similarly to methods known in the art.Formation of the substituted carbocations or silylium in situ occurs ina similar manner to stable salts, but within the vessel and at thedesired temperature of polymerization. The advantage of the latterprocedure is that it is capable of producing carbocations or silyliumcations otherwise too unstable to be handled by the first method. Thecation or the precursor to the cation is typically used in 1 to 1 ratioswith the WCA, however ratios of 1 to 100 (C⁺ or Si⁺ to WCA) also work inthe practice of this invention.

A novel aspect of this invention is the active carbocationic catalystcomplex which is formed and which can be represented by the formulae:

wherein each G is independently hydrogen or a hydrocarbyl group,preferably a C₁ to C₁₀₀ aliphatic group, and g is a n integerrepresenting the number of monomer units incorporated into the growingpolymer chain, g is preferably a number greater than or equal to 1,preferably a number from 1 to about 150,000. WCA⁻ is anyweakly-coordinating anion as described above. All other symbols are asdefined above.

Yet another novel aspect of this invention is the active carbocationiccatalyst complex which is formed and which can be represented by theformulae:

wherein each G is independently hydrogen or an aliphatic or aromaticgroup, preferably a C₁ to C₁₀₀ aliphatic group, and g is a n integerrepresenting the number of monomer units incorporated into the growingpolymer chain, g is preferably a number greater than or equal to 1,preferably a number from 1 to about 150,000. WCA⁻ is anyweakly-coordinating anion as described above. All other symbols are asdefined above.Ge, Sb, Pb

In addition cationic compositions of germanium, tin or lead, may be usedin combination with the WCA's described herein. Preferred compositionsinclude those which are represented by the formula:

wherein R₁, R₂ and R₃ are hydrogen, alkyl, aryl, aralkyl groups orderivatives thereof, preferably C₁ to C₃₀ alkyl, aryl, aralkyl groups orderivatives thereof, and R* is Ge, Sn or Pb. In a preferred embodimentthe R groups are a C₁ to C₁₀ alkyl, preferably methyl, ethyl, propyl, orbutyl.Hydrofluorocarbons

Hydrofluorocarbons are preferably used as diluents in the presentinvention, alone or in combination with other hydrofluorocarbons or incombination with other diluents. For purposes of this invention and theclaims thereto, hydrofluorocarbons (“HFC's” or “HFC”) are defined to besaturated or unsaturated compounds consisting essentially of hydrogen,carbon and fluorine, provided that at least one carbon, at least onehydrogen and at least one fluorine are present.

In certain embodiments, the diluent comprises hydrofluorocarbonsrepresented by the formula: C_(x)H_(y)F_(z) wherein x is an integer from1 to 40, alternatively from 1 to 30, alternatively from 1 to 20,alternatively from 1 to 10, alternatively from 1 to 6, alternativelyfrom 2 to 20 alternatively from 3 to 10, alternatively from 3 to 6, mostpreferably from 1 to 3, wherein y and z are integers and at least one.

Illustrative examples include fluoromethane; difluoromethane;trifluoromethane; fluoroethane; 1,1-difluoroethane; 1,2-difluoroethane;1,1,1-trifluoroethane; 1,1,2-trifluoroethane; 1,1,1,2-tetrafluoroethane;1,1,2,2-tetrafluoroethane; 1,1,1,2,2-pentafluoroethane; 1-fluoropropane;2-fluoropropane; 1,1-difluoropropane; 1,2-difluoropropane;1,3-difluoropropane; 2,2-difluoropropane; 1,1,1-trifluoropropane;1,1,2-trifluoropropane; 1,1,3-trifluoropropane; 1,2,2-trifluoropropane;1,2,3-trifluoropropane; 1,1,1,2-tetrafluoropropane;1,1,1,3-tetrafluoropropane; 1,1,2,2-tetrafluoropropane;1,1,2,3-tetrafluoropropane; 1,1,3,3-tetrafluoropropane;1,2,2,3-tetrafluoropropane; 1,1,1,2,2-pentafluoropropane;1,1,1,2,3-pentafluoropropane; 1,1,1,3,3-pentafluoropropane;1,1,2,2,3-pentafluoropropane; 1,1,2,3,3-pentafluoropropane;1,1,1,2,2,3-hexafluoropropane; 1,1,1,2,3,3-hexafluoropropane;1,1,1,3,3,3-hexafluoropropane; 1,1,1,2,2,3,3-heptafluoropropane;1,1,1,2,3,3,3-heptafluoropropane; 1-fluorobutane; 2-fluorobutane;1,l-difluorobutane; 1,2-difluorobutane; 1,3-difluorobutane;1,4-difluorobutane; 2,2-difluorobutane; 2,3-difluorobutane;1,1,1-trifluorobutane; 1,1,2-trifluorobutane; 1,1,3-trifluorobutane;1,1,4-trifluorobutane; 1,2,2-trifluorobutane; 1,2,3-trifluorobutane;1,3,3-trifluorobutane; 2,2,3-trifluorobutane; 1,1,1,2-tetrafluorobutane;1,1,1,3-tetrafluorobutane; 1,1,1,4-tetrafluorobutane;1,1,2,2-tetrafluorobutane; 1,1,2,3-tetrafluorobutane;1,1,2,4-tetrafluorobutane; 1,1,3,3-tetrafluorobutane;1,1,3,4-tetrafluorobutane; 1,1,4,4-tetrafluorobutane;1,2,2,3-tetrafluorobutane; 1,2,2,4-tetrafluorobutane;1,2,3,3-tetrafluorobutane; 1,2,3,4-tetrafluorobutane;2,2,3,3-tetrafluorobutane; 1,1,1,2,2-pentafluorobutane;1,1,1,2,3-pentafluorobutane; 1,1,1,2,4-pentafluorobutane;1,1,1,3,3-pentafluorobutane; 1,1,1,3,4-pentafluorobutane;1,1,1,4,4-pentafluorobutane; 1,1,2,2,3-pentafluorobutane;1,1,2,2,4-pentafluorobutane; 1,1,2,3,3-pentafluorobutane;1,1,2,4,4-pentafluorobutane; 1,1,3,3,4-pentafluorobutane;1,2,2,3,3-pentafluorobutane; 1,2,2,3,4-pentafluorobutane;1,1,1,2,2,3-hexafluorobutane; 1,1,1,2,2,4-hexafluorobutane;1,1,1,2,3,3-hexafluorobutane, 1,1,1,2,3,4-hexafluorobutane;1,1,1,2,4,4-hexafluorobutane; 1,1,1,3,3,4-hexafluorobutane;1,1,1,3,4,4-hexafluorobutane; 1,1,1,4,4,4-hexafluorobutane;1,1,2,2,3,3-hexafluorobutane; 1,1,2,2,3,4-hexafluorobutane;1,1,2,2,4,4-hexafluorobutane; 1,1,2,3,3,4-hexafluorobutane;1,1,2,3,4,4-hexafluorobutane; 1,2,2,3,3,4-hexafluorobutane;1,1,1,2,2,3,3-heptafluorobutane; 1,1,1,2,2,4,4-heptafluorobutane;1,1,1,2,2,3,4-heptafluorobutane; 1,1,1,2,3,3,4-heptafluorobutane;1,1,1,2,3,4,4-heptafluorobutane; 1,1,1,2,4,4,4-heptafluorobutane;1,1,1,3,3,4,4-heptafluorobutane; 1,1,1,2,2,3,3,4-octafluorobutane;1,1,1,2,2,3,4,4-octafluorobutane; 1,1,1,2,3,3,4,4-octafluorobutane;1,1,1,2,2,4,4,4-octafluorobutane; 1,1,1,2,3,4,4,4-octafluorobutane;1,1,1,2,2,3,3,4,4-nonafluorobutane; 1,1,1,2,2,3,4,4,4-nonafluorobutane;1-fluoro-2-methylpropane; 1,1-difluoro-2-methylpropane;1,3-difluoro-2-methylpropane; 1,1,1-trifluoro-2-methylpropane;1,1,3-trifluoro-2-methylpropane; 1,3-difluoro-2-(fluoromethyl)propane;1,1,1,3-tetrafluoro-2-methylpropane;1,1,3,3-tetrafluoro-2-methylpropane;1,1,3-trifluoro-2-(fluoromethyl)propane;1,1,1,3,3-pentafluoro-2-methylpropane;1,1,3,3-tetrafluoro-2-(fluoromethyl)propane;1,1,1,3-tetrafluoro-2-(fluoromethyl)propane; fluorocyclobutane;1,1-difluorocyclobutane; 1,2-difluorocyclobutane;1,3-difluorocyclobutane; 1,1,2-trifluorocyclobutane;1,1,3-trifluorocyclobutane; 1,2,3-trifluorocyclobutane;1,1,2,2-tetrafluorocyclobutane; 1,1,3,3-tetrafluorocyclobutane;1,1,2,2,3-pentafluorocyclobutane; 1,1,2,3,3-pentafluorocyclobutane;1,1,2,2,3,3-hexafluorocyclobutane; 1,1,2,2,3,4-hexafluorocyclobutane;1,1,2,3,3,4-hexafluorocyclobutane; 1,1,2,2,3,3,4-heptafluorocyclobutane;and mixtures thereof and including mixtures of unsaturated HFC'sdescribed below. Particularly preferred HFC's include difluoromethane,trifluoromethane, 1,1-difluoroethane, 1,1,1-trifluoroethane,fluoromethane, and 1,1,1,2-tetrafluoroethane.

Illustrative examples of unsaturated hydrofluorocarbons include vinylfluoride; 1,1-difluoroethene; 1,2-difluoroethene; 1,1,2-trifluoroethene;1-fluoropropene, 1,1-difluoropropene; 1,2-difluoropropene;1,3-difluoropropene; 2,3-difluoropropene; 3,3-difluoropropene;1,1,2-trifluoropropene; 1,1,3-trifluoropropene; 1,2,3-trifluoropropene;1,3,3-trifluoropropene; 2,3,3-trifluoropropene; 3,3,3-trifluoropropene;1-fluoro-1-butene; 2-fluoro-1-butene; 3-fluoro-1-butene;4-fluoro-1-butene; 1,1-difluoro-1-butene; 1,2-difluoro-1-butene;1,3-difluoropropene; 1,4-difluoro-1-butene; 2,3-difluoro-1-butene;2,4-difluoro-1-butene; 3,3-difluoro-1-butene; 3,4-difluoro-1-butene;4,4-difluoro-1-butene; 1,1,2-trifluoro-1-butene;1,1,3-trifluoro-1-butene; 1,1,4-trifluoro-1-butene;1,2,3-trifluoro-1-butene; 1,2,4-trifluoro-1-butene;1,3,3-trifluoro-1-butene; 1,3,4-trifluoro-1-butene;1,4,4-trifluoro-1-butene; 2,3,3-trifluoro-1-butene;2,3,4-trifluoro-1-butene; 2,4,4-trifluoro-1-butene;3,3,4-trifluoro-1-butene; 3,4,4-trifluoro-1-butene;4,4,4-trifluoro-1-butene; 1,1,2,3-tetrafluoro-1-butene;1,1,2,4-tetrafluoro-1-butene; 1,1,3,3-tetrafluoro-1-butene;1,1,3,4-tetrafluoro-1-butene; 1,1,4,4-tetrafluoro-1-butene;1,2,3,3-tetrafluoro-1-butene; 1,2,3,4-tetrafluoro-1-butene;1,2,4,4-tetrafluoro-1-butene; 1,3,3,4-tetrafluoro-1-butene;1,3,4,4-tetrafluoro-1-butene; 1,4,4,4-tetrafluoro-1-butene;2,3,3,4-tetrafluoro-1-butene; 2,3,4,4-tetrafluoro-1-butene;2,4,4,4-tetrafluoro-1-butene; 3,3,4,4-tetrafluoro-1-butene;3,4,4,4-tetrafluoro-1-butene; 1,1,2,3,3-pentafluoro-1-butene;1,1,2,3,4-pentafluoro-1-butene; 1,1,2,4,4-pentafluoro-1-butene;1,1,3,3,4-pentafluoro-1-butene; 1,1,3,4,4-pentafluoro-1-butene;1,1,4,4,4-pentafluoro-1-butene; 1,2,3,3,4-pentafluoro-1-butene;1,2,3,4,4-pentafluoro-1-butene; 1,2,4,4,4-pentafluoro-1-butene;2,3,3,4,4-pentafluoro-1-butene; 2,3,4,4,4-pentafluoro-1-butene;3,3,4,4,4-pentafluoro-1-butene; 1,1,2,3,3,4-hexafluoro-1-butene;1,1,2,3,4,4-hexafluoro-1-butene; 1,1,2,4,4,4-hexafluoro-1-butene;1,2,3,3,4,4-hexafluoro-1-butene; 1,2,3,4,4,4-hexafluoro-1-butene;2,3,3,4,4,4-hexafluoro-1-butene; 1,1,2,3,3,4,4-heptafluoro-1-butene;1,1,2,3,4,4,4-heptafluoro-1-butene; 1,1,3,3,4,4,4-heptafluoro-1-butene;1,2,3,3,4,4,4-heptafluoro-1-butene; 1-fluoro-2-butene;2-fluoro-2-butene; 1,1-difluoro-2-butene; 1,2-difluoro-2-butene;1,3-difluoro-2-butene; 1,4-difluoro-2-butene; 2,3-difluro-2-butene;1,1,1-trifluoro-2-butene; 1,1,2-trifluoro-2-butene;1,1,3-trifluoro-2-butene; 1,1,4-trifluoro-2-butene;1,2,3-trifluoro-2-butene; 1,2,4-trifluoro-2-butene;1,1,1,2-tetrafluoro-2-butene; 1,1,1,3-tetrafluoro-2-butene;1,1,1,4-tetrafluoro-2-butene; 1,1,2,3-tetrafluoro-2-butene;1,1,2,4-tetrafluoro-2-butene; 1,2,3,4-tetrafluoro-2-butene;1,1,1,2,3-pentafluoro-2-butene; 1,1,1,2,4-pentafluoro-2-butene;1,1,1,3,4-pentafluoro-2-butene; 1,1,1,4,4-pentafluoro-2-butene;1,1,2,3,4-pentafluoro-2-butene; 1,1,2,4,4-pentafluoro-2-butene;1,1,1,2,3,4-hexafluoro-2-butene; 1,1,1,2,4,4-hexafluoro-2-butene;1,1,1,3,4,4-hexafluoro-2-butene; 1,1,1,4,4,4-hexafluoro-2-butene;1,1,2,3,4,4-hexafluoro-2-butene; 1,1,1,2,3,4,4-heptafluoro-2-butene;1,1,1,2,4,4,4-heptafluoro-2-butene; and mixtures thereof and includingmixtures of saturated HFC's described above.

In one embodiment, the diluent comprises non-perfluorinated compounds orthe diluent is a non-perfluorinated diluent. Perfluorinated compoundsbeing those compounds consisting of carbon and fluorine. However, inanother embodiment, when the diluent comprises a blend, the blend maycomprise perfluorinated compound, preferably, the catalyst, monomer, anddiluent are present in a single phase or the aforementioned componentsare miscible with the diluent as described in further detail below. Inanother embodiment, the blend may also comprise chlorofluorocarbons(CFC's), or those compounds consisting of chlorine, fluorine, andcarbon.

In another embodiment, when higher weight average molecular weights (Mw)(typically greater than 10,000 Mw, preferably more than 50,000 Mw, morepreferably more than 100,000 Mw) are desired, suitable diluents includehydrofluorocarbons with a dielectric constant of greater than 10 at −85°C., preferably greater than 15, more preferably greater than 20, morepreferably greater than 25, more preferably 40 or more. In embodimentswhere lower molecular weights (typically lower than 10,000 Mw,preferably less than 5,000 Mw, more preferably less than 3,000 Mw) aredesired the dielectric constant may be less than 10, or by adding largeramounts of initiator or transfer agent when the dielectric constant isabove 10. The dielectric constant of the diluent ε_(D) is determinedfrom measurements of the capacitance of a parallel-plate capacitorimmersed in the diluent [measured value C_(D)], in a reference fluid ofknown dielectric constant ε_(R) [measured value C_(R)], and in air(ε_(A)=1) [measured value C_(A)]. In each case the measured capacitanceC_(M) is given by C_(M)=εC_(C)+C_(S), where ε is the dielectric constantof the fluid in which the capacitor is immersed, C_(C) is the cellcapacitance, and C_(S) is the stray capacitance. From these measurementsε_(D) is given by the formulaε_(D)=((C_(D)−C_(A))ε_(R)+(C_(R)−C_(D)))/(C_(R)−C_(A)). Alternatively, apurpose-built instrument such as the Brookhaven Instrument CorporationBIC-870 may be used to measure dielectric constant of diluents directly.A comparison of the dielectric constants (ε) of a few selected diluentsat −85° C. is provided below and graphically depicted in FIG. 1. Diluentε at −85° C. Methyl chloride 18.34 Difluoromethane 36.291,1-difluoroethane 29.33 1,1,1-trifluoroethane 22.181,1,1,2-tetrafluoroethane 23.25 1,1,2,2-tetrafluoroethane 11.271,1,1,2,2-pentafluoroethane 11.83

In other embodiments, one or more HFC's are used in combination withanother diluent or mixtures of diluents. Suitable additional diluentsinclude hydrocarbons, especially hexanes and heptanes, halogenatedhydrocarbons, especially chlorinated hydrocarbons and the like. Specificexamples include but are not limited to propane, isobutane, pentane,methycyclopentane, isohexane, 2-methylpentane, 3-methylpentane,2-methylbutane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2-methylhexane,3-methylhexane, 3-ethylpentane, 2,2-dimethylpentane,2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethyl pentane,2-methylheptane, 3-ethylhexane, 2,5-dimethylhexane,2,24,-trimethylpentane, octane, heptane, butane, ethane, methane,nonane, decane, dodecane, undecane, hexane, methyl cyclohexane,cyclopropane, cyclobutane, cyclopentane, methylcyclopentane,1,1-dimethylcycopentane, cis 1,2-dimethylcyclopentane,trans-1,2-dimethylcyclopentane, trans-1,3-dimethylcyclopentane,ethylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene,xylene, ortho-xylene, para-xylene, meta-xylene, and the halogenatedversions of all of the above, preferably the chlorinated versions of theabove, more preferably fluorinated versions of all of the above.Brominated versions of the above are also useful. Specific examplesinclude, methyl chloride, methylene chloride, ethyl chloride, propylchloride, butyl chloride, chloroform and the like.

In another embodiment, non-reactive olefins may be used as diluents incombination with HFC's. Examples include, but are not limited to,ethylene, propylene, and the like.

In one embodiment, the HFC is used in combination with a chlorinatedhydrocarbon such as methyl chloride. Additional embodiments includeusing the HFC in combination with hexanes or methyl chloride andhexanes. In another embodiment the HFC's are used in combination withone or more gases inert to the polymerization such as carbon dioxide,nitrogen, hydrogen, argon, neon, helium, krypton, zenon, and/or otherinert gases that are preferably liquid at entry to the reactor.Preferred gases include carbon dioxide and/or nitrogen.

In another embodiment the HFC's are used in combination with one or morenitrated alkanes, including C₁ to C₄₀ nitrated linear, cyclic orbranched alkanes. Preferred nitrated alkanes include, but are notlimited to, nitromethane, nitroethane, nitropropane, nitrobutane,nitropentane, nitrohexane, nitroheptane, nitrooctane, nitrodecane,nitrononane, nitrododecane, nitroundecane, nitrocyclomethane,nitrocycloethane, nitrocyclopropane, nitrocyclobutane,nitrocyclopentane, nitrocyclohexane, nitrocycloheptane,nitrocyclooctane, nitrocyclodecane, nitrocyclononane,nitrocyclododecane, nitrocycloundecane, nitrobenzene, and the di- andtri-nitro versions of the above. A preferred embodiment is HFC's blendedwith nitromethane.

The HFC is typically present at 1 to 100 volume % based upon the totalvolume of the diluents, alternatively between 5 and 100 volume %,alternatively between 10 and 100 volume %, alternatively between 15 and100 volume %, alternatively between 20 and 100 volume %, alternativelybetween 25 and 100 volume %, alternatively between 30 and 100 volume %,alternatively between 35 and 100 volume %, alternatively between 40 and100 volume %, alternatively between 45 and 100 volume %, alternativelybetween 50 and 100 volume %, alternatively between 55 and 100 volume %,alternatively between 60 and 100 volume %, alternatively between 65 and100 volume %, alternatively between 70 and 100 volume %, alternativelybetween 75 and 100 volume %, alternatively between 80 and 100 volume %,alternatively between 85 and 100 volume %, alternatively between 90 and100 volume %, alternatively between 95 and 100 volume %, alternativelybetween 97 and 100 volume %, alternatively between 98 and 100 volume %,and alternatively between 99 and 100 volume %.

In a preferred embodiment the HFC is blended with one or morechlorinated hydrocarbons. In another preferred embodiment the HFC isselected from the group consisting of difluormethane, trifluormethane,1,1-difluoroethane, 1,1,1-trifluoroethane, and 1,1,1,2-tetrafluoroethaneand mixtures thereof. In another preferred embodiment the HFC isselected from the group consisting of monofluoromethane,difluoromethane, trifluoromethane, monofluoroethane, 1,1-difluoroethane,1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,1,2,2,pentafluoroethane, and mixtures thereof. In yet another preferredembodiment the HFC is selected from the group consisting ofmonofluoromethane, difluoromethane, and trifluoromethane.

In another embodiment the diluent or diluent mixture is selected basedupon its solubility in the polymer. Certain diluents are soluble in thepolymer. Preferred diluents have little to no solubility in the polymer.Solubility in the polymer is measured by forming the polymer into a filmof thickness between 50 and 100 microns, then soaking it in diluent(enough to cover the film) for 4 hours at −75° C. The film is removedfrom the diluent, exposed to room temperature for 90 seconds toevaporate excess diluent from the surface of the film, and weighed. Themass uptake is defined as the percentage increase in the film weightafter soaking. The diluent or diluent mixture is chosen so that thepolymer has a mass uptake of less than 4 wt %, preferably less than 3 wt%, preferably less than 2 wt %, preferably less than 1 wt %, morepreferably less than 0.5 wt %.

In a preferred embodiment, the diluent or diluent mixture is selectedsuch that the difference between the measured glass transitiontemperature Tg of the polymer with less than 0.1 wt % of any diluent,unreacted monomers and additives is within 15° C. of the Tg of thepolymer measured after it has been formed into a film of thicknessbetween 50 and 100 microns, that has been soaked in diluent (enough tocover the film) for 4 hours at −75° C. The glass transition temperatureis determined by differential scanning calorimetry (DSC). Techniques arewell described in the literature, for example, B. Wunderlich, “TheNature of the Glass Transition and its Determination by ThermalAnalysis”, in Assignment of the Glass Transition, ASTM STP 1249, R. J.Seyler, Ed., American Society for Testing and Materials, Philadelphia,1994, pp. 17-31. The sample is prepared as described above, sealedimmediately after soaking into a DSC sample pan, and maintained at atemperature below −80° C. until immediately before the DSC measurement.Preferably the Tg values are within 12° C. of each other, preferablywithin 11° C. of each other, preferably within 10° C. of each other,preferably within 9° C. of each other, preferably within 8° C. of eachother, preferably within 7° C. of each other, preferably within 6° C. ofeach other, preferably within 5° C. of each other, preferably within 4°C. of each other, preferably within 3° C. of each other, preferablywithin 3° C. of each other, preferably within 2° C. of each other,preferably within 1° C. of each other.

Polymerization Process

The invention may be practiced in continuous and batch processes.Further the invention may be practiced in a plug flow reactor and/orstirred tank reactors. In particular this invention may be practiced in“butyl reactors.” Illustrative examples include any reactor selectedfrom the group consisting of a continuous flow stirred tank reactor, aplug flow reactor, a moving belt or drum reactor, a jet or nozzlereactor, a tubular reactor, and an autorefrigerated boiling-poolreactor.

In a preferred embodiment, the processes of the present invention arepracticed with a bayonette cooled slurry reactor system. Such reactorsystems have been described, for example, in SU 1627243 A1, RU 2097122C1, and RU 2209213 C1. In particular embodiments, bayonette cooledslurry reactor systems are generally characterized in that they compriseone or more mixer shaft(s) with one or more impeller(s), generally,located in the center of the polymerization reactor vessel, along withone or more bayonette(s). The bayonette may comprise one tube or aplurality or bundle of tubes. The bundle of tubes are used for thecirculation of cooling media, such as refrigerant and/or water, and arelocated, for example, on the periphery of the vessel.

In an embodiment, the upper and lower mixers are located at a distanceof 0.1-0.5 of the impeller diameter from the corresponding head of thevessel.

In certain embodiments, the bayonette reactor system is arrangedaccording to the following. In FIG. 4, the reactor comprises a cylinder1 with concentric mixer comprising a shaft 3 with attached impellers 5,7, 9. The impellers are rotated by a drive 11. Tubular bundles 13 areinstalled on the periphery of the vessel. During polymerization, theyare filled with cooled refrigerant, such as ethane, propane, propylene,ethylene and the like. The refrigerant is circulated through the tubularbundles using nozzles 15 and 17. The nozzles 19 and 21 in the lower headof the vessel are used for addition of feed and catalyst system to thereactor. Nozzle 23 is for the removal of the polymer from the reactor.

When the reactor is operating, the impellers 9 create the required highdegree of mixing of the main body of the reactor mixture and create highflow velocity through the tube bundles 13 and, therefore, intensiveremoval of the heat of reaction. In some embodiments, the bottomimpeller 5 is installed no more than 0.1-0.5 impeller diameters from thebottom head. This assures intensive premixing of the monomer mixturefeed stream and catalyst system that are introduced through nozzles 19and 21 respectively.

In some embodiments, the impeller 7 is installed at the same distance(0.1-0.5 impeller diameters) from the upper head of the vessel,preventing accumulation of the polymer particles in the upper part ofthe reactor, resulting from the fact that the density of the polymer islower than the density of the polymerization medium.

In another aspect of the invention, FIG. 5 shows a reactor havingconfiguration, an intense dispersion of the catalyst system is achieveddue to the high turbulence generated by impeller 28. The bayonette 30 isalso more easily removed for maintenance given that it extends beyondthe dome of the reactor 32. 35 and 37 are lines that provide for thecirculation of the cooling medium. 25 is the line that carries themonomer mixture feed stream into the reactor. 33 is the reactor outlet.29 and 31 are instruments and optionally provided to measure thepolymerization medium temperature. As shown, 29 and 31 are optimallylocated adjacent to impellers 26 and at the main body of the reactor.

In another aspect of the invention, the catalyst system or catalystsystem components may be delivered through a catalyst delivery tube 59as shown in FIG. 6. The catalyst delivery tube 59, the open end of whichis located in the annular space between the bundles 49 and mixer 45. Ina preferred embodiment, the open end of the catalyst delivery tube islocated near the blade tip of mixer 45. In an embodiment, the catalystdelivery tube may be arranged at angle to the housing axis 39 with openend, directed downward, as shown in FIG. 6. In these embodiments, anintense dispersion of the catalyst system is achieved by the placementof the catalyst delivery tube. Thus, polymer formed demonstrate improvedhomogeneity and composition consistency.

In another aspect of the invention, FIG. 6 also shows a verticalcross-section of a reactor. FIG. 7 shows a horizontal cross section ofthe reactor in FIG. 6. FIG. 8 shows a schematically enlarged crosssection of a bayonette tube bundle shown in FIG. 7. The reactorcomprises a housing 39, a shaft 41, mixers 43, 45, and 47, bundles oftubes 49 with tube boards 51, 53 and tube baffles 55, 81 respectively toeach corresponding figure. The reactor vessel 39 is equipped withconnecting pipes 57 for delivery of the monomer mixture, a reactoroutlet 61, catalyst entry nozzles 59, 69, respectively to eachcorresponding figure, and catalyst delivery tubes 63, 71 respectively toeach corresponding figure. The connecting pipe for delivery of thecatalyst is supplied with a catalyst delivery tube 63, 71, respectivelyto each corresponding figure, the open end 73 of which is arranged inthe space between the bundles of tubes 49 and the mixer/impeller 45. Thetube baffle 81 has openings 83 in the spaces 85 between the bundlesectors 87.

The reactor operates in the following manner. A cooling medium isdelivered to the tube bundles on the bottom 65 and emerges from the toppart of the bundles. The monomer feed and catalyst system are deliveredto the reactor from below, and the reactor operates full ofpolymerization medium. The mixers rotate and provide the intensivemixing necessary during polymerization to distribute the polymerizationmedium and to dissipate the heat of reaction during transverse flowaround the heat-exchange tubes of the bundles. The polymer product isremoved from the upper part of the reactor.

The embodiments described in this section may be combined with theplacement of the catalyst delivery tube as shown in FIG. 6. Installationof the catalyst-delivery tube in this manner improves the dispersion ofthe catalyst system within the polymerization medium. Thus, thepolymerization processes of the present invention provide for at leastone of an increase of the length of the cycle and stabilization ofpolymerization, which in turn, enhances the quality of the resultingpolymer.

In any of the previous embodiments and in another aspect of theinvention, as shown in FIG. 6, arranging the lower tube boards and tubebaffles of the bundles at levels and in the immediate vicinity of themixer blades, that is, in the high-velocity flow zones, eliminatesstagnant regions in the area of the tube boards or sheets and tubebaffles. As a result, such an arrangement reduces the clogging of theintertube space by the polymer. Thus, placing the mixers so that thepolymerization medium is directed to the stagnant region of thebayonette tube bundles eliminates agglomeration of the polymer andsupports heat exchange by the bayonette.

In another aspect of the invention, the reactor comprises a bayonettearranged with tube baffles comprising openings as shown in FIGS. 7 and8. The openings may be arranged in the spaces(channels) between thesectors of the bayonette tubes. The openings provide additional pathwaysfor the polymer to migrate to the upper part of reactor to be collected.

The cooling media, as referred to above, may comprise any material thatmay be chilled to a temperature below the desired operating temperatureof the bayonette slurry reactor polymerization medium and has sufficientthermal capacity to remove the polymerization heat of reaction. Thecooling media may pass through the bayonette(s) as a single liquid orgas phase, or may enter the bayonette as a liquid and be partially orcompletely evaporated as it passes through the bayonette. In preferredembodiments, the cooling media comprises refrigerant(s). Suitableexamples of refrigerant(s) include C₁ to C₃₀ alkanes and mixturesthereof, alternatively, C₁ to C₁₀ alkanes and mixtures thereof.Illustrative examples include methane, ethane, and propane, and mixturesthereof. In other preferred embodiments, other suitable examples includeC₂ to C₃₀ alkenes, alternatively, C₂ to C₁₀ alkenes. Illustrativeexamples include ethylene, propylene, and mixtures thereof. In stillother preferred embodiments, other suitable examples include C₁ to C₁₀halogenated alkanes, especially fluorinated alkanes. Illustrativeexamples include methyl fluoride, carbon tetrafluoride, methylenefluoride, trifluoromethane, 1,1,1,2,2 pentafluoroethane, 1,1,1trifluoroethane, fluoroethane and mixtures thereof

Water, alcohols, glycols and mixtures of these may also be used as longas they have freezing temperatures lower than the desired temperature ofthe polymerization medium. In addition, cryogenic liquids may be used.Illustrative examples include nitrogen, helium, argon, and mixturesthereof.

In another aspect, heat can be removed by use of heat transfer surfaces,such as in a tubular reactor where a coolant is on one side of the tubeand the polymerizing mixture is on the other side.

This invention may also be practiced in batch reactors where themonomers, diluent, and catalyst are charged to the reactor and thenpolymerization proceeds to completion (such as by quenching) and thepolymer is then recovered.

In certain embodiments, the invention is practiced using a slurrypolymerization process. However, other polymerization methods arecontemplated such as a solution polymerization process. Thepolymerization processes of the invention may be cationic polymerizationprocesses.

In one embodiment, the polymerization is carried out where the catalyst,monomer, and diluent are present in a single phase. Preferably, thepolymerization is carried-out in a continuous polymerization process inwhich the catalyst, monomer(s), and diluent are present as a singlephase. In slurry polymerization, the monomers, catalyst(s), andinitiator(s) are all miscible in the diluent or diluent mixture, i.e.,constitute a single phase, while the polymer precipitates from thediluent with good separation from the diluent. Desirably, reduced or nopolymer “swelling” is exhibited as indicated by little or no Tgsuppression of the polymer and/or little or no diluent mass uptake asshown in FIG. 2. Thus, polymerization in the diluents of the presentinvention provides for high polymer concentration to be handled at lowviscosity with good heat transfer, reduced reactor fouling, homogeneouspolymerization and/or the convenience of subsequent reactions to be rundirectly on the resulting polymer mixture.

The reacted monomers within the reactor form part of a slurry. In oneembodiment, the concentration of the solids in the slurry is equal to orgreater than 10 vol %. In another embodiment, the concentration ofsolids in the slurry is present in the reactor equal to or greater than25 vol %. In yet another embodiment, the concentration of solids in theslurry is less than or equal to 75 vol %. In yet another embodiment, theconcentration of solids in slurry is present in the reactor from 1 to 70vol %. In yet another embodiment, the concentration of solids in slurryis present in the reactor from 5 to 70 vol %. In yet another embodiment,the concentration of solids in slurry concentration is present in thereactor from 10 to 70 vol %. In yet another embodiment, theconcentration of solids in slurry concentration is present in thereactor from 15 to 70 vol %. In yet another embodiment, theconcentration of solids in slurry concentration is present in thereactor from 20 to 70 vol %. In yet another embodiment, theconcentration of solids in slurry concentration is present in thereactor from 25 to 70 vol %. In yet another embodiment, theconcentration of solids in slurry concentration is present in thereactor from 30 to 70 vol %. In yet another embodiment, theconcentration of solids in slurry concentration is present in thereactor from 40 to 70 vol %.

Typically, a continuous flow stirred tank-type reactor may be used. Thereactor is generally fitted with an efficient agitation means, such as aturbo-mixer or impeller(s), an external cooling jacket and/or internalcooling tubes and/or coils, or other means of removing the heat ofpolymerization to maintain the desired reaction temperature, inlet means(such as inlet pipes) for monomers, diluents and catalysts (combined orseparately), temperature sensing means, and an effluent overflow oroutflow pipe which withdraws polymer, diluent and unreacted monomersamong other things, to a holding drum or quench tank. Preferably, thereactor is purged of air and moisture. One skilled in the art willrecognize proper assembly and operation.

The reactors are preferably designed to deliver good mixing of thecatalyst and monomers within the reactor, good turbulence across orwithin the heat transfer tubes or coils, and enough fluid flowthroughout the reaction volume to avoid excessive polymer accumulationor separation from the diluent.

Other reactors that may be utilized in the practice of the presentinvention include any conventional reactors and equivalents thereofcapable of performing a continuous slurry process. The reactor pumpimpeller can be of the up-pumping variety or the down-pumping variety.The reactor will contain sufficient amounts of the catalyst system ofthe present invention effective to catalyze the polymerization of themonomer containing feed-stream such that a sufficient amount of polymerhaving desired characteristics is produced. The feed-stream in oneembodiment contains a total monomer concentration greater than 5 wt %(based on the total weight of the monomers, diluent, and catalystsystem), preferably greater than 15 wt %, greater than 30 wt % inanother embodiment. In yet another embodiment, the feed-stream willcontain from 5 wt % to 50 wt % monomer concentration based on the totalweight of monomer, diluent, and catalyst system.

In some embodiments, the feed-stream is substantially free from silicacation producing species. By substantially free of silica cationproducing species, it is meant that there is no more than 0.0005 wt %based on the total weight of the monomers of these silica cationproducing species in the feed stream. Typical examples of silica cationproducing species are halo-alkyl silica compounds having the formulaR₁R₂R₃SiX or R₁R₂SiX₂, etc., wherein “R” is an alkyl and “X” is ahalogen. The reaction conditions will be such that desirabletemperature, pressure and residence time are effective to maintain thereaction medium in the liquid state and to produce the desired polymershaving the desired characteristics. The monomer feed-stream is typicallysubstantially free of any impurity which is adversely reactive with thecatalyst under the polymerization conditions. For example, In someembodiments, the monomer feed preferably should be substantially free ofbases (such as caustic), sulfur-containing compounds (such as H₂S, COS,and organo-mercaptans, e.g., methyl mercaptan, ethyl mercaptan),nitrogen-containing bases, oxygen containing bases such as alcohols andthe like. However monomer feed may be less pure, typically not less than95% based on total olefinic content, more preferably not less than 98%,not less than 99%. In preferred embodiments the impurities are presentat less than 10,000 ppm (by weight), preferably less that 500 ppm,preferably less than 250 ppm, preferably less than 150 ppm, preferablyless than 100 ppm.

As is normally the case, reaction time, temperature, concentration, thenature of the reactants, and similar factors determine product molecularweights. The polymerization reaction temperature is convenientlyselected based on the target polymer molecular weight and the monomer tobe polymerized as well as standard process variable and economicconsiderations, e.g., rate, temperature control, etc. The temperaturefor the polymerization is less than 0°0 C., preferably between −10° C.and the freezing point of the slurry in one embodiment, and from −25° C.to −120° C. in another embodiment. In yet another embodiment, thepolymerization temperature is from −40° C. to −100° C., and from −70° C.to −100° C. in yet another embodiment. In yet another desirableembodiment, the temperature range is from −80° C. to −100° C.Consequently, different reaction conditions will produce products ofdifferent molecular weights. Synthesis of the desired reaction productmay be achieved, therefore, through monitoring the course of thereaction by the examination of samples taken periodically during thereaction; a technique widely employed in the art.

In a preferred embodiment, the polymerization temperature is within 10°C. above the freezing point of the diluent, preferably within 8° C.above the freezing point of the diluent, preferably within 6° C. abovethe freezing point of the diluent, preferably within 4° C. above thefreezing point of the diluent, preferably within 2° C. above thefreezing point of the diluent, preferably within 1° C. above thefreezing point of the diluent. For the purposes of this invention andthe claims thereto when the phrase “within X° C. above the freezingpoint of the diluent” is used it means the freezing point of the diluentplus X° C. For example if the freezing point of the diluent is −98° C.,then 10° C. above the freezing point of the diluent is −88° C.

The reaction pressure will be from above 0 to 14,000 kPa in oneembodiment (where 0 kPa is a total vacuum), from 7 kPa to 12,000 kPa inanother embodiment, from 100 kPa to 2000 kPa in another embodiment, from200 kPa to 1500 kPa in another embodiment, from 200 kPa to 1200 kPa inanother embodiment, and from 200 kPa to 1000 kPa in yet anotherembodiment, from 7 kPa to 100 kPa in another embodiment, from 20 kPa to70 kPa in another embodiment, from 40 kPa to 60 kPa in yet anotherembodiment, from 1000 kPa to 14,000 kPa in another embodiment, from 3000kPa to 10,000 kPa in another embodiment, and from 3,000 kPa to 6,000 kPain yet another embodiment.

The order of contacting the monomer feed-stream, catalyst, initiator,and diluent may vary from one embodiment to another.

In another embodiment, the initiator and Lewis acid are pre-contacted bymixing together in the selected diluent for a prescribed amount of timeranging from 0.01 second to 10 hours, and then is injected into thecontinuous reactor through a catalyst nozzle or injection apparatus. Inyet another embodiment, Lewis acid and the initiator are added to thereactor separately. In another embodiment, the initiator is blended withthe feed monomers before injection to the reactor. Desirably, themonomer is not contacted with the Lewis acid, or the Lewis acid combinedwith the initiator before the monomers enter the reactor.

In an embodiment of the invention, the initiator and Lewis acid areallowed to pre-contact by mixing together in the selected diluent attemperatures between −40° C. and the freezing point temperature of thediluent, with a contact time between 0.01 seconds and several hours, andbetween 0.1 seconds and 5 minutes, preferably less than 3 minutes,preferably between 0.2 seconds and 1 minute before injection into thereactor.

In another embodiment of the invention, the initiator and Lewis mid areallowed to pre-contact by mixing together in the selected diluent attemperatures between 80 and −150° C., typically between −40° C. and −98°C.

The overall residence time in the reactor can vary, depending upon,e.g., catalyst activity and concentration, monomer concentration, feedinjection rate, production rate, reaction temperature, and desiredmolecular weight, and generally will be between about a few seconds andfive hours, and typically between about 10 and 60 minutes. Variablesinfluencing residence time include the monomer and diluent feedinjection rates and the overall reactor volume.

The catalyst (Lewis acid) to monomer ratio utilized will be thoseconventional in this art for carbocationic polymerization processes. Inone embodiment of the invention, the monomer to catalyst mole ratioswill typically be from 500 to 10000, and in the range of 2000 to 6500 inanother embodiment. In yet another desirable embodiment, the ratio ofLewis acid to initiator is from 0.5 to 10, or from 0.75 to 8. Theoverall concentration of the initiator in the reactor is typically from5 to 300 ppm or 10 to 250 ppm. The concentration of the initiator in thecatalyst feed stream is typically from 50 to 3000 ppm in one embodiment.Another way to describe the amount of initiator in the reactor is by itsamount relative to the polymer. In one embodiment, there is from 0.25 to20 moles polymer/mole initiator, and from 0.5 to 12 mole polymer/moleinitiator in another embodiment.

The reactor will contain sufficient amounts of the catalyst system ofthe present invention to catalyze the polymerization of the monomercontaining feed-stream such that a sufficient amount of polymer havingdesired characteristics is produced. The feed-stream in one embodimentcontains a total monomer concentration greater than 20 wt % (based onthe total weight of the monomers, diluent, and catalyst system), greaterthan 25 wt % in another embodiment. In yet another embodiment, thefeed-stream will contain from 30 wt % to 50 wt % monomer concentrationbased on the total weight of monomer, diluent, and catalyst system.

Catalyst efficiency (based on Lewis acid) in the reactor is maintainedbetween 10,000 pounds of polymer per pound of catalyst and 300 pounds ofpolymer per pound of catalyst and desirably in the range of 4000 poundsof polymer per pound of catalyst to 1000 pounds of polymer per pound ofcatalyst by controlling the molar ratio of Lewis acid to initiator.

In one embodiment, the polymerization of cationically polymerizablemonomers (such as polymerization of isobutylene and isoprene to formbutyl rubber) comprises several steps. First, a reactor having a pumpimpeller capable of up-pumping or down-pumping is provided. The pumpimpeller is typically driven by an electric motor with a measurableamperage. The reactor typically is equipped with parallel verticalreaction tubes within a jacket containing liquid ethylene. The totalinternal volume, including the tubes, is greater than 30 to 50 liters,thus capable of large scale volume polymerization reactions. The reactortypically uses liquid ethylene to draw the heat of the polymerizationreaction away from the forming slurry. The pump impeller keeps aconstant flow of slurry, diluent, catalyst system and unreacted monomersthrough the reaction tubes. A feed-stream of the cationicallypolymerizable monomer(s) (such as isoprene and isobutylene) in a polardiluent is charged into the reactor, the feed-stream containing lessthan 0.0005 wt % of cation producing silica compounds, and typicallyfree of aromatic monomers. The catalyst system is then charged into thereactor, the catalyst system having a Lewis acid and an initiatorpresent in a molar ratio of from 0.50 to 10.0. Within the reactor, thefeed-stream of monomers and catalyst system are allowed to contact oneanother, the reaction thus forming a slurry of polymer (such as butylrubber), wherein the solids in the slurry has a concentration of from 20vol % to 50 vol %. Finally, the thus formed polymer (such as butylrubber) is allowed to exit the reactor through an outlet or outflow linewhile simultaneously allowing the feed-stream charging to continue, thusconstituting the continuous slurry polymerization. Advantageously, thepresent invention improves this process in a number of ways, e.g., byultimately reducing the amount of polymer accumulation on the reactorwalls, heat transfer surfaces, agitators and/or impeller(s), and in theoutflow line or exit port, as measured by pressure inconsistencies or“jumps.”

In one embodiment, the resultant polymer from one embodiment of theinvention is a polyisobutylene/isoprene polymer (butyl rubber) that hasa molecular weight distribution of from about 2 to 5, and anunsaturation of from 0.5 to 2.5 mole per 100 mole of monomer. Thisproduct may be subjected to subsequent halogenation to afford ahalogenated butyl rubber.

In another embodiment this invention relates to:

-   -   A. A polymerization process comprising contacting one or more        monomers, one or more Lewis acids and one or more initiators in        the presence of a diluent comprising one or more        hydrofluorocarbons (HFC's):    -   B. The process of paragraph A, wherein the diluent comprises 1        to 100 volume % HFC based upon the total volume of the diluent;    -   C. The process of Paragraph A or B, wherein the HFC has a        dielectric constant of 21 or more at −85° C.;    -   D. The process of any of paragraphs A, B or C, wherein the        polymer has a diluent mass uptake of less than 4 wt %;    -   E. The process of any of paragraphs A, B, C, or D, wherein the        diluent further comprises a hydrocarbon;    -   F. The process of any of paragraphs A, B, C, D, or E, wherein        the initiator is selected from the group consisting of hydrogen        halides, a carboxylic acids, water, tertiary alkyl halides, and        mixtures thereof;    -   G. The process of any of paragraphs A, B, C, D, E, or F, wherein        the monomers are selected from the group consisting of styrene,        para-methylstyrene, alpha-methylstyrene, divinylbenzene,        diisopropenylbenzene, isobutylene, 2-methyl-1-butene,        3-methyl-1-butene, 2-methyl-2-pentene, isoprene, butadienes,        2,3-dimethyl-1,3-butadiene, β-pinene, myrcene,        6,6-dimethyl-fulvene, hexadienes, cyclopentadiene, methyl        cyclopentadiene, piperylene, methyl vinyl ether, ethyl vinyl        ether, isobutyl vinyl ether, and mixtures thereof;    -   H. The process of any of paragraphs A, B, C, D, E, F, or G,        where styrenic block copolymers are present in the contacting        step;    -   I. The process of any of paragraphs A, B, C, D, E, F, G, or H,        wherein the temperature is 0° C. or lower;    -   J. The process any of paragraphs A, B, C, D, E, F, G, H, or I,        wherein the temperature is within 10° C. above the freezing        point of the diluent;    -   K. The process of any of paragraphs A, B, C, D, E, F, G, H, I,        or J, wherein the slurry is substantially absent of water;    -   L. The process of any of paragraphs A, B, C, D, E, F, G, H, I, J        or K, wherein the temperature is between −105° C. and −60° C.,        preferably −80° C.;    -   M. The process of any of paragraphs A, B,C, D, E, F, G, H, I, J,        or L, wherein the process comprises an initiator greater than 30        ppm water (based upon weight); and    -   N. The product produced by any of paragraphs A, B, C, D, E, F,        G, H, I, J, K, L, or M.    -   O. A bayonette cooled reactor system utilized with any of the        preceding processes to produce any of the preceding polymers.    -   P. A bayonette cooled slurry reactor system utilized (use) with        any of the preceding processes to produce any of the preceding        polymers.

INDUSTRIAL APPLICATIONS

The polymers of the invention provide chemical and physicalcharacteristics that make them highly useful in wide variety ofapplications. The low degree of permeability to gases accounts for thelargest uses of these polymers, namely inner tubes and tire innerliners.These same properties are also of importance in air cushions, pneumaticsprings, air bellows, accumulator bags, and pharmaceutical closures. Thethermal stability of the polymers of the invention make them ideal forrubber tire-curing bladders, high temperature service hoses, andconveyor belts for hot material handling.

The polymers exhibit high damping and have uniquely broad damping andshock absorption ranges in both temperature and frequency. They areuseful in molded rubber parts and find wide applications in automobilesuspension bumpers, auto exhaust hangers, and body mounts.

The polymers of the instant invention are also useful in tire sidewallsand tread compounds. In sidewalls, the polymer characteristics impartgood ozone resistance, crack cut growth, and appearance. The polymers ofthe invention may also be blended. Properly formulated blends with highdiene rubbers that exhibit phase co-continuity yield excellentsidewalls. Improvements in wet, snow, and ice skid resistances and indry traction without compromises in abrasion resistance and rollingresistance for high performance tires can be accomplished by using thepolymers of the instant invention.

Blends of the polymers of the invention with thermoplastic resins areused for toughening of these compounds. High-density polyethylene andisotactic polypropylene are often modified with 5 to 30 wt % ofpolyisobutylene. In certain applications, the instant polymers providefor a highly elastic compound that is processable in thermoplasticmolding equipment. The polymers of the instant invention may also beblended with polyamides to produce other industrial applications.

The polymers of the instant invention may also be used as adhesives,caulks, sealants, and glazing compounds. They are also useful asplasticizers in rubber formulations with butyl, SBR, and natural rubber.In linear low density polyethylene (LLDPE) blends, they induce cling tostretch-wrap films. They are also widely employed in lubricants asdispersants and in potting and electrical cable filling materials.

In certain applications, the polymers of the invention make them alsouseful in chewing-gum, as well as in medical applications such aspharmaceutical stoppers, and the arts for paint rollers.

The following examples reflect embodiments of the invention and are byno means intended to be limiting of the scope of the invention.

EXAMPLES

The polymerizations were performed glass reaction vessels, equipped witha teflon turbine impeller on a glass stir shaft driven by an externalelectrically driven stirrer. The size and design of the glass vessels isnoted for each set of examples. The head of the reactor included portsfor the stir shaft, thermocouple and addition of initiator/coinitiatorsolutions. The reactor was cooled to the desired reaction temperature,listed in the Tables, by immersing the assembled reactor into a pentaneor isohexane bath in the dry box. The temperature of the stirredhydrocarbon bath was controlled to ±2° C. All apparatus in liquidcontact with the reaction medium were dried at 120° C. and cooled in anitrogen atmosphere before use. Isobutylene (Matheson or ExxonMobil) andmethyl chloride (Air Products) were dried by passing the gas throughthree stainless steel columns containing barium oxide and were condensedand collected as liquids in the dry box. Alternatively, methyl chloridewas dried by passing the gas through stainless steel columns containingsilica gel and molecular sieves. Both materials were condensed andcollected as liquids in the dry box. Isoprene (Aldrich) was dried overcalcium hydride and distilled under Argon. p-Methylstyrene (Aldrich) wasdried over calcium hydride and distilled under vacuum. TMPCl(2-chloro-2,4,4,-trimethylpentane) was prepared from2,4,4-trimethylpentene-1 and a 2.0 mol/L solution of HCl in diethylether. The TMPCl was distilled before use. The HCl (Aldrich, 99% pure)stock solution was prepared by dissolving a desirable amount of HCl gasin dry MeCl to achieve 2-3% concentration by weight. Thehydrofluorocarbons that were collected as clear, colorless liquids at−95° C. were used as received. Hydrofluorocarbons that remained cloudyor had visible insoluble precipitates at −95° C. were distilled beforeuse. Propane (Aldrich), used as received, was condensed and used as aliquid. Alkylaluminum dichlorides (Aldrich) were used as hydrocarbonsolutions. These solutions were either purchased or prepared from theneat alkylaluminum dichloride.

The slurry copolymerizations were performed by dissolving monomer andcomonomer into the liquefied hydrofluorocarbon at polymerizationtemperature and stirred at a pre-determined stirring speed between 800to 1000 rpm. The use of a processor controlled electric stirring motorallowed control of the stirring speed to within 5 rpm. Theinitiator/coinitiator solutions were prepared either in thehydrofluorocarbon or, for convenience of small-scale experiments, in asmall volume of methyl chloride. The initiator/coinitiator solutionswere prepared by dissolving the initiator into the diluent (specified ineach of the examples) and adding, with mixing, a 1.0 M solution of thealkylaluminum halide. The initiator/coinitiator solution was usedimmediately. The initiator/coinitiator solution was added dropwise tothe polymerization using a chilled glass Pasteur pipette or, optionally,a jacketed dropping funnel for examples using the 500 ml glass reactionvessels. When a second or third initiator/coinitiator addition isspecified in the examples, we refer to the preparation and addition of asecond or third batch of freshly prepared initiator/coinitiator solutionidentical in volume and concentrations to the first batch. The physicalbehavior of the rubber particles and the state of fouling was determinedat the end of the addition of each catalyst batch by stopping andremoving the stir shaft and probing the particles with a chilledspatula. Stirring was begun again and the reaction quenched with theaddition of greater than 100 microliters of methanol. Conversion isreported as weight percent of the monomers converted to polymer.

Polymer molecular weights were determined by SEC (Size ExclusionChromatography) using a Waters Alliance 2690 separations module equippedwith column heaters and a Waters 410 differential refractometerdetector. Tetrahydrofuran was used as eluent (1 ml/min., 35° C.) with aset of Waters Styragel HR 5μ columns of 500, 1000, 2000, 10⁴, 10⁵ and10⁶ Å pore size. A calibration based on narrow molecular weightpolyisobutylene standards (American Polymer Standards) was used tocalculate molecular weights and distributions.

Polymer molecular weights can be determined on other SEC instrumentsusing different calibration and run protocols. The methodolgy of SEC(also know as GPC or gel permeation chromatography) to characterizepolymer molecular weights has been reviewed in many publications. Onesuch source is the review provided by L. H. Tung in Polymer Yearbook,H.-G. Elias and R. A. Pethrick, Eds., Harwood Academic Publishers, NewYork, 1984, pgs. 93-100, herein incorporated by reference.

Comonomer incorporation was determined by ¹H-NMR spectrometry. NMRmeasurements were obtained at a field strength corresponding to 400 MHzor 500 MHz. ¹H-NMR spectra were recorded at room temperature on a BrukerAvance NMR spectrometer system using CDCl₃ solutions of the polymers.All chemical shifts were referenced to TMS.

A variety of NMR methods have been used to characterize comonomerincorporation and sequence distribution in copolymers. Many of thesemethods may be applicable to the polymers of this invention. A generalreference which reviews the application of NMR spectrometry to thecharacterization of polymers is H. R. Kricheldorf in Polymer Yearbook,H.-G. Elias and R. A. Pethrick, Eds., Harwood Academic Publishers, NewYork, 1984, pgs. 249-257, herein incorporated by reference.

Table 1 lists the results of polymerizations conducted at −90 to −95° C.in hydrofluorocarbons and methyl chloride (CH₃Cl) (Example 10) andpropane (Example 11) for comparison. A 100 ml glass mini-resin kettlewas used for these examples. TMPCl (2-chloro-2,4,4-trimethylpentane) wasused as an initiator in these examples. TABLE 1^(a) Con- Ex- Temp. Yieldversion M_(w) M_(w)/ Mol % ample (° C.) Diluent (g) (Wt. %) ×10⁻³ M_(n)IP  1^(b) −95 CH₃F 0.80 21.1 225 2.4 1.2  2^(c,d) −93 CH₂F₂ 3.28 83 3053.1 1.7  3 −90 CH₂F₂ 0.99 24.8 297 3.4 1.5  4 −95 CHF₃ 1.88 47.1 390 4.62.2  5^(c) −95 CH₃CHF₂ 1.48 37.3 842 2.5 1.4  6^(c,d) −95 CH₃CF₃ 2.8972.1 327 2.3 2.0  7^(c) −95 CH₂FCF₃ 1.48 37.3 384 2.5 1.7  8^(c) −95CHF₂CHF₂ 0.82 41.0 142 2.3 2.3  9^(c,e) −95 CHF₂CF₃ 0.39 29.3 106 2.82.6 10 −90 CH₃Cl 0.58 14.5 397 3.3 1.3 11 −95 Propane 2.37^(c) 59.4 672.4 2.0^(a)Except where noted polymerizations were run with 30 ml of diluent,5.4 ml of isobutylene and 0.23 ml of isoprene (IP),initiator/coinitiator solutions were prepared in 1.3 ml of methylchloride using 1.6 microliters of TMPCl and 11.5 microliters of a 1.0 Mhexane solution of methylaluminum dichloride (MADC).^(b)Three initiator/coinitiator batches added to the reactor^(c)Two initiator/coinitiator batches added to the reactor^(d)ethylaluminum chloride (EADC) used in place of MADC^(e)reaction scaled to 10 ml of diluent

Polymerization in any of the hydrofluorocarbons resulted in rubberparticles that did not adhere to the walls of the reactor or to thestirring shaft. The particles floated to the surface of the liquid whenstirring stopped. The particles were hard as evidenced by pressing onthem with a chilled spatula when tested near action temperature.Polymerization in methyl chloride resulted in rubber particles thatadhered to both the reactor walls and the stirring shaft. The particleswere clearly rubbery when probed with a chilled spatula when tested nearreaction temperature. Polymerization in propane resulted in a two-phaseliquid-liquid reaction. The denser phase was clearly rich in polymerwhere as the lighter phase was rich in propane.

Examples 12-14

Results for polymerizations conducted at −50 to −55° C. are given inTable 2. Examples 13 and 14 are comparative examples. A 100 ml glassmini-resin kettle was used for these examples. TMPCl(2-chloro-2,4,4-trimethylpentane) was used as an initiator in theseexamples. TABLE 2^(a) Ex- am- Temp. Yield Conversion M_(w) M_(w)/ Mol %ple (C.) Diluent (g) (Wt. %) ×10⁻³ M_(n) IP 12 −55 CH₂F₂ ^(b) 1.1 29.0205 2.2 1.9 13 −50 CH₃Cl 1.1 29.0 52 1.5 1.1 14 −55 Propane^(b) 1.2 30.987 2.2 1.8^(a)Polymerizations were run with 30 ml of diluent, 5.4 ml ofisobutylene and 0.23 ml of isoprene (IP), initiator/coinitiatorsolutions were prepared in 1.3 ml of methyl chloride using 1.6microliters of TMPCl and 11.5 microliters of a 1.0 M hexane solution ofmethylaluminum dichloride^(b)Two initiator/coinitiator batches added to the reactor

The polymerization in difluoromethane gave rubber particles thatexhibited stiff-rubbery physical properties as evidenced by probing witha chilled spatula at reaction temperature. Minor amounts of fouling wereevident on the reactor walls and stirring shaft. In comparison, thepolymerization in methyl chloride resulted in a viscous coating ofpolymer on both the reactor walls and the stirring shaft. Very little ofthe polymer was “suspended” in the diluent medium. The propane basedpolymerization experiment did not look appreciably different than therun at −95° C. (Table 1, Example 11). Two phases were apparent in thereactor. The denser phase was rich in polymer and the lighter phase richin propane. The polymer in the presence of the propane diluent wasconsiderably less viscous than the polymer formed in the methyl chloriderun.

Examples 15-21

Table 3 lists the results of polymerizations conducted at −95° C. inhydrofluorocarbon/methyl chloride blends. A 100 ml glass mini-resinkettle was used for these examples. TMPCl(2-chloro-2,4,4-trimethylpentane) was used as an initiator in theseexamples. TABLE 3^(a) Conversion M_(w) Example Diluents Vol % Yield (g)(Wt. %) ×10⁻³ M_(w)/M_(n) Mol % IP 15 CH₃Cl/CH₂FCF₃ 95/5  2.97 74.0 2343.5 1.2 16 CH₃Cl/CH₂FCF₃ 90/10 1.90 47.0 600 2.9 1.6 17 CH₃Cl/CH₂FCF₃85/15 2.58 64.0 435 2.5 1.3 18 CH₃Cl/CH₂FCF₃ 85/15 1.83 46.0 570 2.5 1.719 CH₃Cl/CH₂FCF₃ 80/20 1.85 46.6 285 2.7 1.5 20 CH₃Cl/CH₂F₂ 80/20 3.2280.0 312 3.2 1.9 21 CH₃Cl/CH₃CF₃ 80/20 2.83 70.6 179 2.7 2.2^(a)Except where noted polymerizations were run with 30 ml of diluent,5.4 ml of isobutylene and 0.23 ml of isoprene (IP),initiator/coinitiator solutions were prepared in 2.6 ml of methylchloride using 3.2 microliters of TMPCl and 23.0 microliters of a 1.0 Mhexane solution of ethylaluminum dichloride (EADC)^(b)methylaluminum dichloride (MADC) used instead of ethylaluminumdichloride (EADC)

Examples 22-25

Results for polymerizations conducted at −55° C. are given in Table 4.Two batches of initiator/coinitiator solutions were used for eachexample. A 100 ml glass mini-resin kettle was used for these examples.TMPCl (2-chloro-2,4,4-trimethylpentane) was used as an initiator inthese examples. TABLE 4^(a) Conversion M_(w) Example Diluents Vol %Yield (g) (Wt. %) ×10⁻³ M_(w)/M_(n) Mol % IP 22 CH₃Cl/CH₂FCF₃ 90/10 2.3561.7 84 1.7 2.2 23 CH₃Cl/CH₂FCF₃ 85/15 2.96 77.7 77 2.2 2.2 24CH₃Cl/CH₂FCF₃ 80/20 2.37 62.2 82 1.9 2.0 25 CH₃Cl/CH₂FCF₃ 75/25 2.3862.5 88 2.0 2.2^(a)Polymerizations were run with 30 ml of diluent, 5.4 ml ofisobutylene and 0.23 ml of isoprene (IP), initiator/coinitiatorsolutions were prepared in 1.3 ml of methyl chloride using 1.6microliters of TMPCl and 11.5 microliters of a 1.0 M hexane solution ofmethylaluminum dichloride (MADC).

A polymerization was conducted with methoxyaluminum dichloride at −95°C. The initiator/coinitiator solution was prepared by dissolving 0.93microliters of anhydrous methanol into 2.6 ml of liquid1,1,1,2-tetrafluoroethane at −35° C. To this solution was added 23microliters of a 1.0 mol/L solution of ethylaluminum dichloride inpentane. This solution was stirred for 10 minutes. A second solution wasprepared in the same way. To each solution, 3.2 microliters of2-chloro-2,4,4-trimethylpentane was added with stirring and cooled −95°C. Both solutions were added dropwise to the polymerization solutionwith a chilled pipette. A 100 ml glass mini-resin kettle was used forthis example. TABLE 5 Yield Conversion M_(w) Mol % Example Diluent (g)(Wt. %) ×10⁻³ M_(w)/M_(n) IP 26 CH₂FCF₃ 2.61 65 248 2.6 2.6

Table 6 lists the results of a polymerization conducted at −95° C.conducted in an 85/15 (V/V) blend of 1,1,1,2-tetrafluoroethane and1,1-difluoroethane. This run was made with 30 ml of diluent, 5.4 ml ofisobutylene, 0.26 ml of isoprene and used a initiator/coinitiatorsolution prepared in 2.6 ml methyl chloride using 3.2 microliters ofTMPCl and 32.0 microliters of a 1.0 M hexane solution of methylaluminumdichloride (MADC). A 100 ml glass mini-resin kettle was used for thisexample. TABLE 6 Conversion M_(w) Example Yield (g) (Wt. %) ×10⁻³M_(w)/M_(n) Mol % IP 27 0.28 7 772 2.8 1.8

Examples 28-31

Table 7 lists the results of polymerizations that were conducted at −95°C. in hydrofluorocarbons and a blend of a hydrofluorocarbon and methylchloride using p-methylstyrene (pMS) as a comonomer. A 100 ml glassmini-resin kettle was used for these examples. TMPCl(2-chloro-2,4,4-trimethylpentane) was used as an initiator in theseexamples. TABLE 7^(a) Ex- Yield Conversion M_(w) M_(w)/ Mol % ampleDiluent (g) (Wt. %) ×10⁻³ M_(n) pMS 28 CH₂FCF₃ 1.37 33 322 3.2 2.1 29CH₃Cl/CH₂FCF₃ 0.96 23 762 4.2 2.2 80/20 V/V 30^(b) CH₂FCF₃ 3.81 92 1603.3 3.6 31^(b,c) CH₂FCF₃ 1.18 28 278 3.2 1.8^(a)Except where noted polymerizations were run with 30 ml of diluent,5.4 ml of isobutylene and 0.34 ml of p-methylstyrene,initiator/coinitiator solutions were prepared in 2.6 ml of methylchloride using 3.2 microliters of TMPCl and 23.0 microliters of a 1.0 Mhexane solution of ethylaluminum dichloride (EADC).^(b)32.0 microliters of a 1.0 M hexane solution of ethylaluminumdichloride was used instead of the amount noted in (a) above.^(c)1.6 microliters of 2-chloro-2-methylpropane used in place of theTMPCl used in (a).

Polymerization in any of the diluents of Table 7 resulted in rubberparticles that did not adhere to the walls of the reactor or to thestirring shaft. The particles floated to the surface of the liquid whenstirring stopped. When tested near the reaction temperature, theparticles were hard as evidenced by pressing on them with a chilledspatula.

Examples 32-37

Table 8 lists the results of polymerizations that were conducted at −95°C. in hydrofluorocarbons and methyl chloride for comparison. Examples 36and 37 are comparative examples. A three-neck 500 ml glass reactor wasused for these examples. Prior to each polymerization, 300 ml of monomerfeed containing 10 wt % of monomers were charged into the chilledreactor. The initiator/coinitiator molar ratio was controlled at 1/3 andthe concentration was set at 0.1 wt % EADC in MeCl. Theinitiator/coinitiator solution was added dropwise to the polymerizationmixture and the rate of addition is controlled in such as way so thatthe reactor temperature raise did not exceed 4° C. The amount ofinitiator/coinitiator solution added in each depended on the desiredmonomer conversion target. TABLE 8^(a) Conversion M_(n) M_(w) ExampleDiluent (Wt. %) ×10⁻³ ×10⁻³ M_(w)/M_(n) Mol % IP 32 CH₂FCF₃ 65 315 6262.0 2.7 33 CH₂FCF₃ 94 213 489 2.3 3.0 34 CH₃CHF₂ 55 414 813 2.0 1.3 35CH₃CHF₂ 100 197 558 2.8 1.8 36 CH₃Cl 54 170 628 3.7 2.0 37 CH₃Cl 97 135517 3.8 2.4^(a)Polymerizations were run with an isobutylene/isoprene molar feedratio of 95/5

The examples in Table 8 demonstrate the production of high molecularweight butyl rubber using an EADC/HCl initiator system in CHF₂CF₃ andCH₃CHF₂ diluents. The molecular weight of the butyl polymers made inCHF₂CF₃ and CH₃CHF₂ were significantly higher than polymers made in MeClat similar monomer conversion under similar conditions. Thepolydispersity (Mw/Mn) of the butyl polymers made in both CH₂FCF₃ andCH₃CHF₂ was narrower and closer to the most probable polydispersity of2.0 than the polymers made in MeCl under similar experimentalconditions. The isoprene incorporation in the copolymers made in MeClfalls between CH₂FCF₃ and CH₃CHF₂. The polymer slurry particles made inboth CH₂FCF₃ and CH₃CHF₂ appeared to be significantly less sticky duringhandling than the polymer slurry particles made in MeCl under similarconditions.

Examples 38-44

Table 9 lists the results of copolymerizations of isobutylene andp-methylstyrene that were conducted at −95° C. in hydrofluorocarbons andmethyl chloride for comparison. Examples 41 and 42 are comparativeexamples. A three-neck 500 ml glass reactor was used for these examples.Prior to each polymerization, 300 ml of monomer feed containing 10 wt %of monomers were charged into the chilled reactor. Theinitiator/coinitiator molar ratio was controlled at 1/3 and theconcentration was set at 0.1 wt % EADC in MeCl. Theinitiator/coinitiator solution was added dropwise to the polymerizationmixture) and the rate of addition is controlled in such as way so thatthe reactor temperature raise did not exceed 4° C. The amount ofinitiator/coinitiator solution added in each depended on the desiredmonomer conversion target. TABLE 9^(a) Conversion M_(n) M_(w) Mole %Example Diluent (Wt. %) ×10⁻³ ×10⁻³ M_(w)/M_(n) pMS 38 CHF₂CF₃ 22 91 2983.3 4.3 39 CHF₂CF₃ 57 89 291 3.3 4.4 40 CHF₂CF₃ 98 74 244 3.3 4.6 41CH₃CHF₂ 56 188 1,091 5.8 4.1 42 CH₃CHF₂ 100 169 908 5.4 4.9 43 CH₃Cl 5797 443 4.6 3.8 44 CH₃Cl 69 94 342 3.6 4.0^(a)Polymerizations were run with an isobutylene/p-methylstyrene molarfeed ratio of 90/10

The examples in Table 9 demonstrate that using an EADC/HCl initiatorsystem in a CH₂FCF₃ diluent, the production of isobutylene-PMScopolymers with comparable molecular weights to copolymers produced in aMeCl diluent. Isobutylene/p-methylstyrene copolymers prepared in CH₃CHF₂exhibit much higher molecular weights. The pMS incorporation in thecopolymer is significantly higher in CH₂FCF₃ than in MeCl using the samemonomer feed composition under similar reaction conditions. In addition,the polymer slurry particles in CH₂FCF₃ appears to be significantly lesssticky in CH₂FCF₃ than in MeCl.

Examples 45-47

Table 10 lists the results of copolymerizations ofisobutylene/p-methylstyrene and isobutylene/isoprene that were conductedat −95° C. in an 80/20 mixture (by volume) of CH₂FCF₃ and CH₃CHF₂. Athree-neck 500 ml glass reactor was used for these examples. Prior toeach polymerization, 300 ml of monomer feed containing 10 wt % ofmonomers were charged into the chilled reactor. Theinitiator/coinitiator molar ratio was controlled at 1/3 and theconcentration was set at 0.1 wt % EADC in MeCl. Theinitiator/coinitiator solution was added dropwise to the polymerizationmixture and the rate of addition is controlled in such as way so thatthe reactor temperature raise did not exceed 4° C. The amount ofinitiator/coinitiator solution added in each depended on the desiredmonomer conversion target. TABLE 10 Conversion M_(n) M_(w) ExampleComonomer (Wt. %) ×10⁻³ ×10⁻³ M_(w)/M_(n) 45^(a) Isoprene 87 309 676 2.246^(b) pMS 76 449 1,048 2.3 47^(b) PMS 100 349 1,166 3.3^(a)Polymerizations were run with an isobutylene/isoprene molar feedratio of 95/5^(b)Polymerizations were run with an isobutylene/p-methylstyrene molarfeed ratio of 90/10

Table 10 demonstrates the production of high molecular weightisobutylene-isoprene copolymers and isobutylene-pMS copolymers using anEADC/HCl initiator system in a mixture of CH₂FCF₃ and CH₃CHF₂ as thepolymerization diluent. The polymer slurry particles in theCH₂FCF₃/C₃CHF₂ mixture demonstrate the same non-stickiness appearance asin a pure CH₂FCF₃ or CH₃CHF₂ diluent described above.

Examples 48-117

Examples 48-117 exemplify copolymerization of isobutylene with othercomonomers. The copolymerizations have been run at two temperatures andin four diluents.

The polymerization examples listed in Tables 11-16 were obtained byrunning slurry copolymerizations in test tubes equipped with rare earthmagnetic stir bars. Monomer solutions were prepared in the test tubes atthe desired temperature, which is identified in the paragraphs below, bycombining 20 ml of the liquid diluent, 5 ml of liquid isobutylene andenough liquid comonomer to achieve a 3 mol % comonomer feed.Polymerization solutions were magnetically stirred at the identifiedtemperature and were initiated by the dropwise addition of a stockcoinitiator/initiator solution using a chilled glass Pasteur pipette.Conversion is reported as weight percent of the monomers converted topolymer.

Table 11 lists the results of polymerizations that were conducted at−95° C. either in methyl chloride (as a comparative, examples 48, 49,50, 57, 58, 59, 66, 67, and 68), 1,1,1,2-tetrafluoroethane or1,1-difluoroethane. Isobutylene was copolymerized with eitherp-t-butylstyrene (t-BuS) (0.36 ml per run), indene (Ind) (0.23 ml perrun) or β-pinene (βP) (0.31 ml per run) as indicated in Table 18. Astock solution of ethylaluminum dichloride (EADC) and hydrogen chloride(HCl) was prepared in methyl chloride by adding 0.320 ml of a 1.0 mol/LHCl solution in 1,1,1,2-tetrafluoroethane and 0.960 ml of a 1.0 mol/Lethylaluminum dichloride solution in hexane to 100 ml of methylchloride. Polymerizations were run by adding, dropwise, 1.5 ml of thisstock EADC/HCl solution to the stirred monomer solutions.Polymerizations were terminated with the addition of 0.2 ml of methanol.Polymerization in any of the hydrofluorocarbons resulted in rubberparticles that did not adhere to the walls of the reactor or to thestirring bar. The particles floated to the surface of the liquid whenstirring stopped. The particles were hard as evidenced by pressing onthem with a chilled spatula when tested near reaction temperature.Polymerization in methyl chloride resulted in rubber particles thatadhered to both the reactor walls and the stirring shaft. TABLE 11 YieldConv. M_(w) mol % Example Diluent CoM (mg) (wt. %) ×10⁻³ M_(w)/M_(n) CoM48 CH₃Cl t-BuS 496 12.8 139 2.5 1.4 49 CH₃Cl t-BuS 384 9.6 130 2.3 2.450 CH₃Cl t-BuS 485 12.6 112 2.2 1.5 51 CH₂FCF₃ t-BuS 345 8.9 128 2.0 2.052 CH₂FCF₃ t-BuS 249 6.4 128 2.0 1.6 53 CH₂FCF₃ t-BuS 295 7.6 119 1.91.9 54 CH₃CHF₂ t-BuS 325 8.4 297 2.7 1.8 55 CH₃CHF₂ t-BuS 433 11.2 2172.6 2.3 56 CH₃CHF₂ t-BuS 333 8.6 303 2.7 1.8 57 CH₃Cl Ind 375 9.9 68 2.21.2 58 CH₃Cl Ind 179 4.7 117 1.7 1.3 59 CH₃Cl Ind 130 3.4 103 2.3 1.1 60CH₂FCF₃ Ind 2279 60.8 131 2.2 2.3 61 CH₂FCF₃ Ind 1199 31.9 101 2.1 2.462 CH₂FCF₃ Ind 2299 61.3 116 2.2 2.0 63 CH₃CHF₂ Ind 323 14.0 141 2.3 1.864 CH₃CHF₂ Ind 243 9.1 138 2.3 1.8 65 CH₃CHF₂ Ind 526 8.6 146 2.3 1.9 66CH₃Cl βP 402 10.5 20.7 1.0 8.3 67 CH₃Cl βP 406 10.6 20.5 1.1 7.8 68CH₃Cl βP 235 6.2 17.6 1.0 8.9 69 CH₂FCF₃ βP 644 17.7 29.5 1.4 9.4 70CH₂FCF₃ βP 833 22.1 39.7 1.4 8.1 71 CH₂FCF₃ βP 610 16.2 37.0 1.4 8.5

Table 12 lists the results of polymerizations that were conducted at−50° C. either in methyl chloride (as a comparative, examples 72, 73,74, 81, 82, and 83), 1,1,1,2-tetrafluoroethane or 1,1-difluoroethane.Isobutylene was copolymerized with either p-t-butylstyrene (t-BuS) (0.36ml per run) or indene (Ind) (0.23 ml per run) as indicated in Table 12.A stock solution of ethylaluminum dichloride (EADC) and hydrogenchloride (HCl) was prepared in methyl chloride by adding 0.320 ml of a1.0 mol/L HCl solution in 1,1,1,2-tetrafluoroethane and 0.960 ml of a1.0 mol/L ethylaluminum dichloride solution in hexane to 100 ml ofmethyl chloride. Polymerizations were run by adding, dropwise, 1.5 ml ofthis stock EADC/HCl solution to the stirred monomer solutions except forexamples 72, 73, 74, 81, 82, 83 and 87. In examples 72, 73, 74, 81, 82,83, and 87, 2.3 ml of EADC/HCl solution was used. Polymerizations wereterminated with the addition of 0.2 ml of methanol. Polymerization inany of the hydrofluorocarbons resulted in rubber particles that did notadhere to the walls of the reactor or to the stirring bar. The particlesfloated to the surface of the liquid when stirring stopped. Theparticles were much more stiff, as evidenced by pressing on them with achilled spatula when tested near reaction temperature, than with themethyl chloride prepared examples. Polymerization in methyl chlorideresulted in rubber particles that adhered to both the reactor walls andthe stirring shaft. TABLE 12 Yield Conv. M_(w) mol % Example Diluent CoM(mg) (wt. %) ×10⁻³ M_(w)/M_(n) CoM 72 CH₃Cl t-BuS 1750 45.3 48.4 1.7 2.973 CH₃Cl t-BuS 1917 49.6 58.0 1.9 2.9 74 CH₃Cl t-BuS 2758 71.4 60.4 2.02.9 75 CH₂FCF₃ t-BuS 500 12.9 35.3 1.4 4.1 76 CH₂FCF₃ t-BuS 523 13.539.2 1.5 4.3 77 CH₂FCF₃ t-BuS 568 14.7 39.7 1.5 4.3 78 CH₃CHF₂ t-BuS 65116.9 68.1 1.7 4.4 79 CH₃CHF₂ t-BuS 733 19.0 71.9 1.6 4.1 80 CH₃CHF₂t-BuS 440 11.4 70.3 1.7 2.8 81 CH₃Cl Ind 704 18.6 49.9 1.4 1.0 82 CH₃ClInd 645 17.1 34.1 1.4 1.4 83 CH₃Cl Ind 319 8.4 44.6 1.4 1.1 84 CH₂FCF₃Ind 424 11.3 36.7 1.4 1.7 85 CH₂FCF₃ Ind 464 12.4 37.9 1.4 2.0 86CH₂FCF₃ Ind 496 13.2 40.8 1.5 1.9 87 CH₃CHF₂ Ind 328 8.7 40.8 1.5 1.4 88CH₃CHF₂ Ind 338 9.0 42.9 1.5 1.3

Table 13 lists the results of polymerizations that were conducted at−95°0 C. in a 20 wt. % blend of 1,1-difluoroethane in1,1,1,2-tetrafluoroethane. Isobutylene was copolymerized with one of thefollowing comonomers or comonomer pairs as indicated in Table 13:isoprene (IP) (0.20 ml per run), p-methylstyrene (pMS) (0.26 ml perrun), p-t-butylstyrene (t-BuS) (0.36 ml per run), blend (Ind) (0.23 mlper run), β-pinene (βP) (0.31 ml per run) or a 50/50 mol/mol blend(IP/pMS) of isoprene (0.10 ml) and p-methylstyrene (0.13 ml) per run asindicated in Table 20. A stock solution of ethylaluminum dichloride(EADC) and hydrogen chloride (HCl) was prepared in methyl chloride byadding 0.320 ml of a 1.0 mol/L HCl solution in 1,1,1,2-tetrafluoroethaneand 0.960 ml of a 1.0 mol/L ethlyaluminum dichloride solution in hexaneto 100 ml of methyl chloride. Polymerizations were run by adding,dropwise, 1.5 ml of this stock EADC/HCl solution to the stirred monomersolutions, except for examples 98, 99, 100, 101, 102, and 103. Forexamples 98, 99 and 100, 3.0 ml of EADC/HCl solution was used. Forexamples 101, 102 and 103, 2.3 ml of EADC/HCl solution was used.Polymerizations were terminated with the addition of 0.2 ml of methanol.Polymerization in any of the hydrofluorocarbons resulted in rubberparticles that did not adhere to the walls of the reactor or to thestirring bar. The particles floated to the surface of the liquid whenstirring stopped. The particles were hard as evidenced by pressing onthem with a chilled spatula when tested near reaction temperature.Polymerization in methyl chloride resulted in rubber particles thatadhered to both the reactor walls and the stirring shaft. TABLE 13 YieldConv. M_(w) mol % Example CoM (mg) (wt. %) ×10⁻³ M_(w)/M_(n) CoM 89 IP1147 31.1 453 2.0 1.9 90 IP 2061 55.9 628 1.8 2.0 91 IP 2382 64.6 2762.0 2.2 92 pMS 654 17.3 782 3.4 2.8 93 pMS 722 19.1 624 3.0 2.8 94 pMS795 21.0 665 3.0 2.7 95 t-BuS 411 10.6 304 2.0 1.6 96 t-BuS 389 9.8 2522.1 1.9 97 t-BuS 445 11.5 241 2.1 1.9 98 Ind 166 4.4 283 2.2 1.3 99 Ind405 10.7 267 2.3 1.4 100 Ind 208 5.5 317 2.1 1.2 101 βP 1340 35.6 1041.5 5.2 102 βP 375 10.0 79.4 1.4 8.4 103 βP 389 10.4 76.9 1.4 8.8 104IP/pMS 331 8.9 632 1.8 0.49/1.7 105 IP/pMS 423 11.3 699 1.8 0.67/1.5 106IP/pMS 361 9.7 989 2.1 0.71/1.5

Table 14 lists the results of copolymerization of isobutylene andbutadiene (0.15 ml per run) that were conducted at −95° C. in methylchloride (as a comparative, examples 107 and 108),1,1,1,2-tetrafluoroethane, 1,1-difluoroethane or a 20 wt. % blend(CH₃CHF₂/CH₂FCF₃) of 1,1-difluoroethane in 1,1,1,2-tetrafluroethane. Astock solution of ethylaluminum dichloride (EADC) and hydrogen chloride(HCl) was prepared in methyl chloride by adding 0.320 ml of a 1.0 mol/LHCl solution in 1,1,1,2-tetrafluoroethane and 0.960 ml of a 1.0 mol/Lethylaluminum dichloride solution in hexane to 100 ml of methylchloride. Polymerizations were run by the adding, dropwise, 1.5 ml ofthis stock EADC/HCl solution to the stirred monomer solutions.Polymerizations were terminated with the addition of 0.2 ml of methanol.Polymerization in any of the hydrofluorocarbons resulted in rubberparticles that did not adhere to the walls of the reactor or to thestirring bar. The particles floated to the surface of the liquid whenstirring stopped. The particles were hard as evidenced by pressing onthem with a chilled spatula when tested near reaction temperature.Polymerization in methyl chloride resulted in rubber particles thatadhered to both the reactor walls and the stirring shaft. The polymerslisted in Table 14 exhibited molecular weights that were higher than theexclusion limit of the SEC instrument used to determine the molecularweights. The M_(w) of these polymers is above 1.5×10⁶ g/mol. Molecularweight distributions (MWD) could also not be determined for thesesamples cause of the high molecular weight. TABLE 14 Yield Conv. mol %Example Diluent (mg) (wt. %) CoM 107 CH₃Cl 503 13.7 0.2 108 CH₃Cl 68918.8 0.1 109 CH₂FCF₃ 448 12.2 0.2 110 CH₂FCF₃ 543 14.8 0.3 111 CH₂FCF₃404 11.0 0.3 112 CH₃CHF₂ 338 9.2 0.2 113 CH₃CHF₂ 481 13.1 0.1 114CH₃CHF₂ 352 9.6 0.2 115 CH₃CHF₂/CH₂FCF₃ 453 12.4 0.3 116 CH₃CHF₂/CH₂FCF₃777 21.2 0.2 117 CH₃CHF₂/CH₂FCF₃ 573 15.7 0.2

Examples 118-141

The polymerization examples listed in Tables 15 and 16 were obtained byrunning slurry copolymerizations in test tubes equipped with rare earthmagnetic stir bars. Monomer solutions were prepared in the test tubes at−95° C. for examples in Table 15 and −35° C. for examples in Table 16.The solutions were prepared by combining 20 ml of the chilled liquiddiluent, 5 ml of liquid isobutylene and 0.20 ml of isoprene. Exceptionsto this procedure are noted below. Polymerization solutions weremagnetically stirred at temperature and were initiated by the dropwiseaddition of a stock coinitiator/initiator solution using a chilled glassPasteur pipette. Conversion is reported as weight percent of themonomers converted to polymer.

Table 15 lists the results of polymerizations that were conducted at−95° C. Examples 118, 119, 120, 123, 124, 125, and 126 are comparativeexamples with Examples 118 and 119 being examples of this invention.

Polymerizations were run by the dropwise addition of this stock ofethylaluminum dichloride (EADC)/hydrogen chloride (HCl) solution to thestirred monomer solutions. A stock solution of EADC and HCl was preparedin methyl chloride by adding 0.320 ml of a 1.0 mol/L HCl solution in1,1,1,2-tetrafluoroethane and 0.960 ml of a 1.0 mol/L ethylaluminumdichloride solution in hexane to 100 ml of methyl chloride. The totalvolume of the stock solution added to the polymerization for eachexample is listed in Table 15. A separate stock solution ofethylaluminum dichloride and hydrogen chloride was used for Examples 125and 126. This solution was prepared from the addition of 2.0 ml of a0.16 mol/L HCl solution in 1,1,1,2-tetrafluoroethane and 0.960 ml of a1.0 mol/L ethylaluminum dichloride solution in hexane to 100 ml ofmethyl chloride. The final mol/L concentrations of ethylaluminumdichloride and hydrogen chloride in the stock solution is the same forboth preparations. Polymerizations were terminated with the addition of0.2 ml of methanol. Polymerization in 3,3,3-trifluoropropene resulted inrubber particles that did not adhere to the walls of the reactor or tothe stirring bar. The particles floated to the surface of the liquidwhen stirring stopped. The particles were hard as evidenced by pressingon them with a chilled spatula when tested near reaction temperature.Polymerization in methyl chloride resulted in rubber particles thatadhered to both the reactor walls and the stirring shaft. Polymerizationin 1,1-dichloroethane or 1,1-dichloroethene resulted in solvent swollenpolymer particles that adhered to the reactor walls and the stirringbar. TABLE 15 Cat. mol Exam- Soln. Yield Conv. M_(w) % ple Diluent (ml)(mg) (wt. %) ×10⁻³ M_(w)/M_(n) IP 118 CH₃Cl 1.7 844 22.9 271 2.2 1.7 119CH₃Cl 1.7 618 16.7 255 1.9 1.8 120 CH₃Cl 1.7 597 16.2 224 2.2 1.7 121H₂C═CHCF₃ 1.7 309 16.7 266 2.3 2.2 122 H₂C═CHCF₃ 1.7 274 20.6 218 2.11.8 123 H₂C═CCl₂ 1.7 118 3.2 33 1.4 1.4 124 H₂C═CCl₂ 4.0 447 13.4 47 2.11.0 125 CH₃CHCl₂ 1.5 112 3.0 108 3.1 1.7 126 CH₃CHCl₂ 1.5 202 5.5 1162.6 1.9

Table 16 lists the results of polymerizations that were conducted at−35° C. Examples 127-136 are comparative examples with Examples 137-141being examples of this invention.

Polymerizations were run by the dropwise addition of a stock solution ofthe coinitiator/initiator pair. A stock solution of ethylaluminumdichloride and hydrogen chloride (HCl) was prepared in methyl chlorideby adding 0.320 ml of a 1.0 mol/L HCl solution in1,1,1,2-tetrafluoroethane and 0.960 ml of a 1.0 mol/L ethylaluminumdichloride solution in hexane to 100 ml of methyl chloride. A separatestock solution of ethylaluminum dichloride and hydrogen chloride wasused for Examples 134, 135 and 136. This solution was prepared from theaddition of 0.034 ml of a 0.93 mol/L HCl solution in1,1,1,2-tetrafluoroethane and 0.0960 ml of a 1.0 mol/L ethylaluminumdichloride solution in hexane to 10 ml of methyl chloride. The finalmol/L concentrations of ethylaluminum dichloride and hydrogen chloridein the stock solution are the same for both preparations. A separatestock solution of methylaluminum dichloride(MADC)/2-chloro-2,4,4-trimethylpentane (TMPCl) was used for Examples 132and 133. The MADC/T[PC1 solution was prepared from the addition of 6.6microliters of TMPCl and 0.0960 ml of a 1.0 mol/L methylaluminumdichloride solution in hexane to 10 ml of methyl chloride. The totalvolume of the stock solution added to the polymerization for eachexample is listed in Table 16.

Polymerizations were terminated with the addition of 0.2 ml of methanol.The polymerization in 1,1-difluoroethane or 1,1,1,2-tetrafluoroethanegave rubber particles that exhibited stiff-rubbery physical propertiesas evidenced by probing with a chilled spatula at reaction temperature.Minor amounts of fouling were evident on the reactor walls and stirringbar. In comparison, the polymerization in methyl chloride resulted in aviscous coating of polymer on both the reactor walls and the stirringbar. Very little of the polymer was “suspended” in the diluent medium.Polymerization in 1,2-difluorobenzene or 1,2-dichloroethane resulted insolvent swollen polymer phases that adhered to the reactor walls and thestirring bar. Polymerization in 1,1,1-trichloroethane occurred insolution. Polymer was recovered by removing weathering off the solvent.TABLE 16 Cat. Soln. Yield Conv. M_(w) mol % Example Diluent (ml) (mg)(wt. %) ×10⁻³ M_(w)/M_(n) IP 127 CH₃Cl 4.0 1953 53.1 45 1.2 1.2 128CH₃Cl 4.0 1678 45.6 54 1.3 1.3 129 CH₃Cl 4.0 2339 63.6 51 1.2 1.4 130CH₃CCl₃ 4.0 3068 83.2 48 2.2 0.9 131 CH₃CCl₃ 5.0 2993 81.2 59 2.2 1.0132 1,2-difluorobenzene 4.0 2033 55.1 35 1.6 1.5 133 1,2-difluorobenzene4.0 1901 51.6 29 1.8 1.4 134 CH₂ClCH₂Cl 4.0 2563 69.5 29 1.9 1.3 135CH₂ClCH₂Cl 4.0 2707 73.4 24 1.8 1.3 136 CH₂ClCH₂Cl 4.0 2683 72.8 27 1.91.4 137 CH₂FCF₃ 3.0 2348 63.8 76 1.5 2.3 138 CH₂FCF₃ 1.5 1024 27.8 921.5 2.2 139 CH₃CHF₂ 3.0 1085 29.5 78 1.5 1.6 140 CH₃CHF₂ 3.0 1104 30.092 1.4 1.6 141 CH₃CHF₂ 3.0 953 25.9 95 1.5 1.6

Examples 142-146

Table 17 lists the results of copolymerizations of isobutylene isoprenethat were conducted at −95° C. CH₂FCF₃. The isobutylene/isoprene feedratio changed for each example. A three-neck 500 ml glass reactor wasused for these examples. Prior to each polymerization, 300 ml of monomerfeed containing 10 wt % of monomers were charged into the chilledreactor. The initiator/coinitiator molar ratio was controlled at 1/3 andthe concentration was set at 0.1 wt % EADC in MeCl. Theinitiator/coinitiator solution was added dropwise to the polymerizationmixture and the rate of addition is controlled in such as way so thatthe reactor temperature raise did not exceed 4° C. The amount ofinitiator/coinitiator solution added in each depended on the desiredmonomer conversion target. TABLE 17 IB/IP Molar Conversion M_(n) M_(w)Example Feed Ratio (Wt. %) ×10⁻³ ×10⁻³ M_(w)/M_(n) Mol % IP 142 98/2 100209 905 4.3 1.2 143 97/3 100 141 636 4.5 1.7 144 95/5 100 127 481 3.82.9 145 93/7 94 174 423 2.4 3.8 146 90/10 85 133 348 2.6 5.2

These examples demonstrate the preparation of high molecular weightcopolymers with high isoprene incorporation. The agglomeration of theslurry particles is significantly reduced in the hydrofluorocarbon. TheGPC traces of these isobutylene/isoprene copolymers do not show any signof gel formation or cross-linking, even for the Example 146 whichcontains more than 5 mol % isoprene. The high diene isobutylene/isoprenepolymers made according to this invention can be halogenatedsubsequently via standard, established halogenation processes for makinghalobutyl polymers.

Example 147

The dependence of molecular weight on conversion was determined forisobutylene/isoprene copolymerizations run in methyl chloride andCH₂FCF₃ at −95° C. This dependence was determined for two differentinitiator/coinitiator systems; one based on TMPCl and the other based onHCl. Both catalyst systems used EADC as the Lewis acid coinitiator. Athree-neck 500 ml glass reactor was used for these examples. Prior toeach polymerization, 300 ml of monomer feed containing 10 wt % of themonomers were charged into the chilled reactor. A molar ratio of 95/5isobutylene/isoprene was used for each polymerization. Theinitiator/coinitiator molar ratio was controlled at 1/3 and theconcentration was set at 0.1 wt % EADC in MeCl. Theinitiator/coinitiator solution was added dropwise to the polymerizationmixture and the rate of addition is controlled in such as way so thatthe reactor temperature raise did not exceed 4° C. The amount ofinitiator/coinitiator solution added in each depended on the desiredmonomer conversion target. The data for these polymerizations are shownin FIG. 3 as a plot of peak molecular weight (M_(p)) versus the monomerconversion in wt %. The expected decline of molecular weight withincreasing conversion is observed. These data also show that HCl is apreferred initiator for copolymerizations in CH₂FCF₃.

Example 148

A copolymerization of isobutylene and cyclopentadiene was conducted at−93° C. in CH₂FCF₃. A molar ratio of 97/3 of isobutylene/cyclopentadienewas used for this polymerization at 10.8 wt % monomers in the feed.Cyclopentadiene was freshly cracked for this experiment. Theinitiator/coinitiator solution was prepared by dissolving 200microliters of a 1.0 mol/L solution of hydrogen chloride in CH₂FCF₃ into50 ml of pre-chilled CH₂FCF₃. To this solution was added 500 microlitersof a 1.0 mol/L solution of ethylaluminum dichloride in hexane. Thissolution was stirred for 5 minutes. Polymerization was begun by thedropwise addition of the initiator/coinitiator solution into the monomersolution with stirring. The addition of this solution was maintained ata rate necessary to keep the polymerization temperature from risingabove −92° C. A total of 35 ml of the initiator/coinitiator solution wasused. A 500 ml glass resin kettle was used for this example. TABLE 18Conversion M_(w) Mol % Example Diluent (Wt %) ×10⁻³ M_(w)/M_(n) CPD % 1,2 148 CH₂FCF₃ 50 527 1.9 5.3 15Solubility of Ethylaluminum Dichloride in Hydrofluorocarbons and Blends

The solubility tests reported in Tables 19-25 were performed using neatethylaluminum dichloride (EADC). Each test was performed in thefollowing way. 5 ml of the condensed hydrofluorocarbon were charged intoa dried test tube cooled to −90° C. in the dry box cold bath. To thisliquid at −90° C., 4.1 microliters of neat, liquid ethylaluminumdichloride (EADC) was added. Solubility was checked by vigorouslyagitating the resulting mixture. The mixture was then allowed to warm tothe boiling point of the diluent while agitating the contents of thetest tube. After the diluent reached its boiling point, the mixture wascooled to −90° C. by immersing the test tube into the cold bath.Reported observations were made after the completed heating/coolingcycle. If after this first heat/cool cycle, the catalyst aid notdissolve, 0.5 ml of methyl chloride was added. The heat/cool cycle wasrepeated. Subsequent additions of 0.5 ml of methyl chloride were madefollowing each heat/cool cycle until the EADC was observed to dissolveor a 50/50 V/V blend was achieved. The following observations were madeand recorded.

1,1,1,2-Tetrafluoroethane (HFC-134a) TABLE 19 Volume % MethylPreparation Chloride Observation EADC + 5 ml HFC-134a 0 Insoluble‘chips’ + 0.5 ml methyl chloride 9 Fine-scale flocculation + 0.5 mlmethyl chloride 17 Fine-scale flocculation + 0.5 ml methyl chloride 23Cloudy suspension; slight floc at b.p. + 0.5 ml methyl chloride 29Cloudy; very small particles + 0.5 ml methyl chloride 33 Less cloudy; novisible particles + 0.5 ml methyl chloride 38 Still less cloudy + 0.5 mlmethyl chloride 41 Nearly clear + 0.5 ml methyl chloride 44 Nearlyclear + 0.5 ml methyl chloride 47 Clear + 0.5 ml methyl chloride 50Clear

In the tests in Table 19, the flocculation occurred after cessation ofstirring, from a very cloudy suspension. The original ‘chips’ were nolonger visible.

Difluoromethane (HFC-32) TABLE 20 Volume % Methyl Preparation ChlorideObservation EADC + 5 ml HFC-32 0 Insoluble ‘chips’ + 0.5 ml methylchloride 9 Slight cloudy + 0.5 ml methyl chloride 17 Some flocculation +0.5 ml methyl chloride 23 Clear

Fluoroform (HFC-23) TABLE 21 Volume % Methyl Preparation ChlorideObservation EADC + 5 ml HFC-23 0 Insoluble ‘chips’ + 0.5 ml methylchloride 9 Insoluble + 0.5 ml methyl chloride 17 Insoluble + 0.5 mlmethyl chloride 23 Insoluble + 0.5 ml methyl chloride 29 Insoluble + 0.5ml methyl chloride 33 Insoluble + 0.5 ml methyl chloride 38 Insoluble +0.5 ml methyl chloride 41 Insoluble + 0.5 ml methyl chloride 44Insoluble + 0.5 ml methyl chloride 47 Insoluble + 0.5 ml methyl chloride50 Insoluble

1,1,1-Trifluoroethane (HFC-143a) TABLE 22 Volume % Preparation MethylChloride Observation EADC + 5 ml HFC-143a 0 Insoluble ‘chips’ + 0.5 mlmethyl chloride 9 Cloudy suspension + 0.5 ml methyl chloride 17 Cloudysuspension + 0.5 ml methyl chloride 23 Clear solution

1,1-difluroethane (HFC-152a) TABLE 23 Volume % Preparation MethylChloride Observation EADC + 5 ml HFC-152a 0 Soluble

The solubility tests performed in Table 24 were performed using 1.0mol/L stock hydrocarbon solutions of ethylaluminum dichloride (EADC)prepared at room temperature from neat EADC and the hydrocarbon listedin the table. Pentane refers to normal pentane. ULB hexanes refers to anultra low benzene grade of hexanes, an isomeric mixture, which containsless than 5 ppm benzene. The final 1,1,1,2-tetrafluoroethane (HFC-134a)solution was prepared by adding the room temperature EADC stocksolution, volume listed in the table, to the liquid HFC-134a in a testtube held at −35° C. In all cases, an initial solution is obtained whichis clear and colorless. The resulting solution was then cooled byimmersing the test tube into the dry box cold bath thermostated at −95°C. The cloud point was determined by monitoring the temperature of theliquid with a thermometer and visually determining the onset ofcloudiness. The solutions again became clear by allowing the solutionsto warm to a temperature above the cloud point. The behavior of thesolution around the cloud point was observed for several minutes byrepeatedly cooling and warming the solution. This phenomenon was foundto be reproducible. TABLE 24 Volume (microliters) of 1.0 M Volume ofFinal EADC Cloud Stock EADC HFC-134a Concentration Point HydrocarbonSolution (mL) (Wt. %) (° C.) Pentane 100 10 0.1 −87 Pentane 174 15 0.1−87 ULB hexanes 174 15 0.1 −85Solubility of Alkoxyaluminum Dichlorides in 1,1,1,2-tetrafluoroethane(HFC-134a)

The solubility tests reported in Table 25 were conducted by preparingeach alkoxyaluminum dichloride in situ. A general procedure follows. Asolution of the corresponding alcohol was prepared by adding 0.0001moles of the alcohol to 10 milliliters of HFC-134a at −30° C. To thissolution was added 100 microliters of a 1.0 mol/L stock pentane solutionof EADC. After this last addition, the HFC-134a solution was shakenperiodically over the next five minutes. The solution was allowed towarm to −10° C. in a closed vessel and then cooled in the dry box coldbath thermostated at −95° C. The cloud point was determined bymonitoring the temperature of the liquid with a thermometer and visuallydetermining the onset of cloudiness. The solutions again became clear byallowing the solutions to warm to a temperature above the cloud point.The behavior of the solution around the cloud point was observed forseveral minutes by repeatedly cooling and warming the solution. Thisphenomenon was found to be reproducible. TABLE 25 CH₃OAlCl₂ CH₃CH₂OAlCl₂(CH₃)₃COAlCl₂ CF₃CH₂OAlCl₂ FW (g/mol) 128.92 142.95 171.00 196.92 Wt. %0.09 0.10  0.12 0.14 solution @ −40° C. Cloud point (° C.) −85 −85 −85w/solids −87

PROPHETIC EXAMPLES Prophetic Example 1 Methyl Chloride (Comparative)

The process for producing butyl rubber may be conducted using abayonette type slurry reactor configuration such as that depicted inFIGS. 4 through 8.

A mixture of monomers in methyl chloride solution containing 20 wt %isobutylene, 0.55 wt % isoprene and 79.45 wt % methyl chloride may becontinuously fed into a bayonette slurry reactor through a feedinjection nozzle in the amount of 15 T/hr. At the same time, a solutionof aluminum chloride in methyl chloride with a concentration of 0.1 wt %may be fed into the bayonette slurry reactor through a catalystinjection nozzle in the amount of 0.5 T/hr. The reaction mixture may beintensively mixed with the multistage agitator. The reactor may bemaintained full of liquid during the course of the reaction. Thetemperature in the bayonette slurry reactor may be maintained within therange from minus 92 to minus 88° C., registering it with resistancethermometers. The heat of polymerization may be removed from thepolymerizing slurry by vaporizing liquid ethylene at minus 110° C. inthe bayonettes.

The butyl rubber may form a suspension of fine rubber particles suchthat the polymer concentration within the reactor may be about 16 wt %,the polymer unsaturation may be 1.6 mol % (isoprene content), the Mooneyviscosity (1+8 at 125° C.) may be 50±3, and the reactor may be able tooperate continuously for an average of about 30 hours until excessivefouling takes place within the reactor as measured by warmer than minus88° C. slurry temperature and/or excessive power draw from themultistage mixer/agitator. The conversion to polymers of isobutylene inthe feed may be about 80% and of isoprene in the food at about 60% . Thetotal production of butyl rubber in the reactor may be 2.45 T/hr.

Prophetic Example 2 (Inventive)

The process for producing butyl rubber may be conducted in a bayonettetype slurry reactor configuration such as that depicted in FIGS. 4through 8, using 1,1,1,2 tetrafluoroethane (HFC-134a) rather than methylchloride as the diluent for the feed and catalyst steams.

A mixture of monomers in HFC-134a solution containing 30 wt %isobutylene, 0.65 wt % isoprene and 69.35 wt % HFC-134a may becontinuously fed into the bayonette slurry reactor through a feedinjection nozzle in the amount of 15 T/hr. At the same time, a solutionof ethylaluminumdichloride (EADC) and HFC-134a may be mixed to aconcentration of 0.1 wt %, chilled to minus 80° C., and then mixed withthe initiator, anhydrous HCl, to provide a 3.0 mol/mol ratio of EADC/HClto form the catalyst system. The catalyst system may then be fed intothe bayonette slurry reactor through the catalyst injection nozzle inthe amount of 0.3 T/hr. The reaction mixture may be intensively mixedwith a multistage agitator. The reactor may be maintained full of liquidduring the course of the reaction. The temperature in the bayonetteslurry reactor may be maintained within the range from minus 92 to minus88° C., registering it with resistance thermometers. The heat ofpolymerization may be removed from the polymerizing slurry by vaporizingliquid ethylene at minus 110° C. in the bayonettes.

The butyl rubber may form a suspension of fine rubber particles suchthat the polymer concentration within the reactor may be about 27 wt %,the polymer unsaturation may be 1.6 mol%, the Mooney viscosity (1+8 at125° C.) may be 50±3, and the reactor may be able to operatecontinuously for an average of about 60 hours or more until excessivefouling takes place within the reactor as measured by warmer than minus88° C. slurry temperature and/or excessive power draw from themultistage mixer i agitator. The conversion to polymers of isobutylenein the feed may be about 90% and of isoprene in the feed may be about83%. The total production of butyl rubber in the reactor may be 4.12T/hr.

Prophetic Example 3 (Inventive)

The process may be conducted as in Example 2, but the bayonette slurryreactor may be operated at minus 75° C. slurry temperature rather thanminus 90° C. slurry temperature. The boiling ethylene in the bayonettesmay be operated at minus 95° C.

With the feed stream and catalyst system compositions described inExample 2, the catalyst stream flowrate to the reactor may be lowered to0.25 T/hr to form a suspension of fine rubber particles such that thepolymer concentration within the reactor may be about 26 wt %, thepolymer unsaturation may be 1.6 mol %, the Mooney viscosity (1+8 at 125°C.) may be 50±3, and the reactor may be able to operate continuously foran average of at least 45 hours until excessive fouling takes placewithin the reactor as measured by warmer than minus 75° C. slurrytemperature and/or excessive power draw from the multistagemixer/agitator. The conversion to polymers of isobutylene in the feedmay be about 86% and of isoprene in the feed may be about 80%. The totalproduction of butyl rubber in the reactor may be 3.95 T/hr.

Prophetic Example 4 (Inventive)

The process may be conducted as in Example 2, but the hydrofluorocarbondiluent used may be 1,1 difluoroethane (HFC-152a) rather than HFC-134aSimilar reactor production, reactor operability, product quality, andmonomer conversions may be obtained.

Prophetic Example 5 (Inventive)

The process may be conducted as in Example 2, but the feed and catalystdiluent may be a 50 wt %/50 wt % mixture of methyl chloride andHFC-134a. Similar reactor production, reactor operability, productquality, and monomer conversions may be obtained.

All patents and patent applications, test procedures (such as ASTMmethods), and other documents cited herein are fully incorporated byreference to the extent such disclosure is not inconsistent with thisinvention and for all jurisdictions in which such incorporation ispermitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.

While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of theinvention. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present invention,including all features which would be treated as equivalents thereof bythose skilled in the art to which the invention pertains.

1. A process to produce polymers comprising contacting one or moremonomer(s), a catalyst system, and a diluent comprising one or morehydrofluorocarbon(s) (HFC's) in a reactor comprising a bayonette.
 2. Theprocess of claim 1, wherein the process is a slurry polymerizationprocess and the reactor is a tubular reactor.
 3. The process of claim 1,wherein the reactor further comprises a vertical cylindrical housing, anupper part, and a lower part.
 4. The process of claim 3, wherein thereactor further comprises connecting pipes for delivery of the catalystsystem in the lower part, and connecting pipes for the removal of thepolymer in the upper part.
 5. The process of claim 1, wherein thereactor further comprises a shaft with blade mixers mounted along theheight of the shaft.
 6. The process of claim 1, wherein the bayonettecomprises a plurality of tubes.
 7. The process of claim 6, wherein thetubes comprise sectors.
 8. The process of claim 1, wherein the bayonettecomprises tube disks and tube baffles.
 9. The process of claim 8,wherein the tube baffles comprise spaces between the sectors.
 10. Theprocess of claim 8, wherein the tube baffles comprise holes.
 11. Theprocess of claim 8, wherein the reactor comprises a catalyst systemdelivery tube comprising an open end, the open end located in the spacebetween the tube baffles.
 12. The process of claim 11, wherein the openend of the catalyst system delivery tube is angled in a downwarddirection toward a mixer.
 13. The process of claim 8, wherein thereactor comprises one or more catalyst system delivery tube(s)comprising open ends.
 14. The process of claim 13, wherein at least oneopen end is angled in a downward direction toward a mixer.
 15. Theprocess of claim 1, wherein the reactor comprises a mixer locatedadjacent to a tube baffle.
 16. The process of claim 1, wherein the oneor more monomer(s) comprise isobutylene and isoprene.
 17. The process ofclaim 1, where the one or more monomer(s) comprise isobutylene andpara-methylstyrene.
 18. The process of claim 1, wherein one or morehydrofluorocarbon(s) is represented by the formula: C_(x)H_(y)F_(z)wherein x is an integer from 1 to 40 and y and z are integers of one ormore.
 19. The process of claim 18, wherein x is from 1 to
 10. 20. Theprocess of claim 18, wherein x is from 1 to
 6. 21. The process of claim18, wherein x is from 1 to
 3. 22. The process of claim 1, wherein theone or more hydrofluorocarbon(s) is independently selected from thegroup consisting of fluoromethane; difluoromethane; trifluoromethane;fluoroethane; 1,1-difluoroethane; 1,2-difluoroethane;1,1,1-trifluoroethane; 1,1,2-trifluoroethane; 1,1,1,2-tetrafluoroethane;1,1,2,2-tetrafluoroethane; 1,1,1,2,2-pentafluoroethane; 1-fluoropropane;2-fluoropropane; 1,1-difluoropropane; 1,2-difluoropropane;1,3-difluoropropane; 2,2-difluoropropane; 1,1,1-trifluoropropane;1,1,2-trifluoropropane; 1,1,3-trifluoropropane; 1,2,2-trifluoropropane;1,2,3-trifluoropropane; 1,1,1,2-tetrafluoropropane;1,1,1,3-tetrafluoropropane; 1,1,2,2-tetrafluoropropane;1,1,2,3-tetrafluoropropane; 1,1,3,3-tetrafluoropropane;1,2,2,3-tetrafluoropropane; 1,1,1,2,2-nentafluoropronane:1,1,1,2,3-pentafluoropropane; 1,1,1,3,3-pentafluoropropane;1,1,2,2,3-pentafluoropropane; 1,1,2,3,3-pentafluoropropane;1,1,1,2,2,3-hexafluoropropane; 1,1,1,2,3,3-hexafluoropropane;1,1,1,3,3,3-hexafluoropropane; 1,1,1,2,2,3,3-heptafluoropropane;1,1,1,2,3,3,3-heptafluoropropane; 1-fluorobutane; 2-fluorobutane;1,1-difluorobutane; 1,2-difluorobutane; 1,3-difluorobutane;1,4-difluorobutane; 2,2-difluorobutane; 2,3-difluorobutane;1,1,1-trifluorobutane; 1,1,2-trifluorobutane; 1,1,3-trifluorobutane;1,1,4-trifluorobutane; 1,2,2-trifluorobutane; 1,2,3-trifluorobutane;1,3,3-trifluorobutane; 2,2,3-trifluorobutane; 1,1,1,2-tetrafluorobutane;1,1,1,3-tetrafluorobutane; 1,1,1,4-tetrafluorobutane;1,1,2,2-tetrafluorobutane; 1,1,2,3-tetrafluorobutane;1,1,2,4-tetrafluorobutane; 1,1,3,3-tetrafluorobutane;1,1,3,4-tetrafluorobutane; 1,1,4,4-tetrafluorobutane;1,2,2,3-tetrafluorobutane; 1,2,2,4-tetrafluorobutane;1,2,3,3-tetrafluorobutane; 1,2,3,4-tetrafluorobutane;2,2,3,3-tetrafluorobutane; 1,1,1,2,2-pentafluorobutane;1,1,1,2,3-pentafluorobutane; 1,1,1,2,4-pentafluorobutane;1,1,1,3,3-pentafluorobutane; 1,1,1,3,4-pentafluorobutane;1,1,1,4,4-pentafluorobutane; 1,1,2,2,3-pentafluorobutane;1,1,2,2,4-pentafluorobutane; 1,1,2,3,3-pentafluorobutane;1,1,2,4,4-pentafluorobutane; 1,1,3,3,4-pentafluorobutane;1,2,2,3,3-pentafluorobutane; 1,2,2,3,4-pentafluorobutane;1,1,1,2,2,3-hexafluorobutane; 1,1,1,2,2,4-hexafluorobutane;1,1,1,2,3,3-hexafluorobutane, 1,1,1,2,3,4-hexafluorobutane;1,1,1,2,4,4-hexafluorobutane; 1,1,1,3,3,4-hexafluorobutane;1,1,1,3,4,4-hexafluorobutane; 1,1,1,4,4,4-hexafluorobutane;1,1,2,2,3,3-hexafluorobutane; 1,1,2,2,3,4-hexafluorobutane;1,1,2,2,4,4-hexafluorobutane; 1,1,2,3,3,4-hexafluorobutane;1,1,2,3,4,4-hexafluorobutane; 1,2,2,3,3,4-hexafluorobutane;1,1,1,2,2,3,3-heptafluorobutane; 1,1,1,2,2,4,4-heptafluorobutane;1,1,1,2,2,3,4-heptafluorobutane; 1,1,1,2,3,3,4-heptafluorobutane;1,1,1,2,3,4,4-heptafluorobutane; 1,1,1,2,4,4,4-heptafluorobutane;1,1,1,3,3,4,4-heptafluorobutane; 1,1,1,2,2,3,3,4-octafluorobutane;1,1,1,2,2,3,4,4-octafluorobutane; 1,1,1,2,3,3,4,4-octafluorobutane;1,1,1,2,2,4,4,4-octafluorobutane; 1,1,1,2,3,4,4,4-octafluorobutane;1,1,1,2,2,3,3,4,4-nonafluorobutane; 1,1,1,2,2,3,4,4,4-nonafluorobutane;1-fluoro-2-methylpropane; 1,1-difluoro-2-methylpropane;1,3-difluoro-2-methylpropane; 1,1,1-trifluoro-2-methylpropane;1,1,3-trifluoro-2-methylpropane; 1,3-difluoro-2-(fluoromethyl)propane;1,1,1,3-tetrafluoro-2-methylpropane;1,1,3,3-tetrafluoro-2-methylpropane;1,1,3-trifluoro-2-(fluoromethyl)propane;1,1,1,3,3-pentafluoro-2-methylpropane;1,1,3,3-tetrafluoro-2-(fluoromethyl)propane;1,1,1,3-tetrafluoro-2-(fluoromethyl)propane; fluorocyclobutane;1,1-difluorocyclobutane; 1,2-difluorocyclobutane;1,3-difluorocyclobutane; 1,1,2-trifluorocyclobutane;1,1,3-trifluorocyclobutane; 1,2,3-trifluorocyclobutane;1,1,2,2-tetrafluorocyclobutane; 1,1,3,3-tetrafluorocyclobutane;1,1,2,2,3-pentafluorocyclobutane; 1,1,2,3,3-pentafluorocyclobutane;1,1,2,2,3,3-hexafluorocyclobutane; 1,1,2,2,3,4-hexafluorocyclobutane;1,1,2,3,3,4-hexafluorocyclobutane; 1,1,2,2,3,3,4-heptafluorocyclobutaneand mixtures thereof
 23. The process of claim 1, wherein the one or morehydrofluorocarbon(s) is independently selected from monofluoromethane,difluoromethane, trifluoromethane, monofluoroethane, 1,1-difluoroethane,1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,1,2,2,pentafluoroethane, and mixtures thereof.
 24. The process of claims claim1, wherein the diluent comprises from 15 to 100 volume % HFC based uponthe total volume of the diluent.
 25. The process of claim 1, wherein thediluent comprises from 20 to 100 volume % HFC based upon the totalvolume of the diluent.
 26. The process of claim 1, wherein the diluentcomprises from 25 to 100 volume % HFC based upon the total volume of thediluent.
 27. The process of claim 1, wherein the diluent furthercomprises a hydrocarbon, a non-reactive olefin, and/or an inert gas. 28.The process of claim 27, wherein the hydrocarbon is a halogenatedhydrocarbon other than an HFC.
 29. The process of claim 28, wherein thehalogenated hydrocarbon is methyl chloride.
 30. The process of claim 1,wherein the catalyst system comprises one or more Lewis acid(s)represented by the formula MX₄; wherein M is a Group 4, 5, or 14 metal;and each X is a halogen.
 31. The process of claim 1, wherein thecatalyst system comprises one or more Lewis acid(s) represented by theformula MR_(n)X_(4-n); wherein M is Group 4, 5, or 14 metal; each R is amonovalent C₁ to C₁₂ hydrocarbon radical independently selected from thegroup consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkylradicals; n is an integer from 0 to 4; and each X is a halogen.
 32. Theprocess of claim 1, wherein the catalyst system comprises one or moreLewis acid(s) represented by the formula M(RO)_(n)R′_(m)X_(4-(m+n));wherein M is Group 4, 5, or 14 metal; each RO is a monovalent C₁ to C₃₀hydrocarboxy radical independently selected from the group consisting ofan alkoxy, aryloxy, arylalkoxy, alkylaryloxy radicals; each R′ is amonovalent C₁ to C₁₂ hydrocarbon radical independently selected from thegroup consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkylradicals; n is an integer from 0 to 4; m is an integer from 0 to 4,wherein the sum of n and m is not more than 4; and each X is a halogen.33. The process of claim 1, wherein the catalyst system comprises one ormore Lewis acid(s) represented by the formulaM(RC═OO)_(n)R′_(m)X_(4-(m+n)); wherein M is Group 4, 5, or 14 metal;each RC═OO is a monovalent C₂ to C₃₀ hydrocarbacyl radical independentlyselected from the group consisting of an alkacyloxy, arylacyloxy,arylalkylacyloxy, alkylarylacyloxy radicals; each R′ is a monovalent C₁to C₁₂ hydrocarbon radical independently selected from the groupconsisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkylradicals; n is an integer from 0 to 4; m is an integer from 0 to 4,wherein the sum of n and m is not more than 4; and each X is a halogen.34. The process of claim 1, wherein the catalyst system comprises one ormore Lewis acid(s) represented by the formula MOX₃; wherein M is a Group5 metal; and each X is a halogen.
 35. The process of claim 1, whereinthe catalyst system comprises one or more Lewis acid(s) represented bythe formula MX₃; wherein M is a Group 13 metal; and each X is a halogen.36. The process of 29 claim 1, wherein the catalyst system comprises oneor more Lewis acid(s) represented by the formula MR_(n)X_(3-n); whereinM is a Group 13 metal; each R is a monovalent C₁ to C₁₂ hydrocarbonradical independently selected from the group consisting of an alkyl,aryl, arylalkyl, alkylaryl and cycloalkyl radicals; n is an integer from1 to 3; and each X is a halogen.
 37. The process of any claim 1, whereinthe catalyst system comprises one or more Lewis acid(s) represented bythe formula M(RO)_(n)R′_(m)X_(3-(m+n)); wherein M is a Group 13 metal;each RO is a monovalent C₁ to C₃₀ hydrocarboxy radical independentlyselected from the group consisting of an alkoxy, aryloxy, arylalkoxy,alkylaryloxy radicals; each R′ is a monovalent C₁ to C₁₂ hydrocarbonradical independently selected from the group consisting of an alkyl,aryl, arylalkyl, alkylaryl and cycloalkyl radicals; n is an integer from0 to 3; m is an integer from 0 to 3, wherein the sum of n and m is from1 to 3; and each X is a halogen.
 38. The process of claim 1, wherein thecatalyst system comprises one or more Lewis acid(s) represented by theformula M(RC═OO)_(n)R′_(ml X) _(3-(m+n)); wherein M is a Group 13 metal;each RC═OO is a monovalent hydrocarbacyl radical independently selectedfrom the group independently selected from the C₂ to C₃₀ groupconsisting of an alkacyloxy, arylacyloxy, arylalkylacyloxy,alkylarylacyloxy radicals; each R′ is a monovalent C₁ to C₁₂ hydrocarbonradical independently selected from the group consisting of an alkyl,aryl, arylalkyl, alkylaryl and cycloalkyl radicals; n is an integer from0 to 3; m is a integer from 0 to 3, wherein the sum of n and m is from 1to 3; and each X is a halogen.
 39. The process of claim 1, wherein thecatalyst system comprises one or more Lewis acid(s) represented by theformula MX_(y); wherein M is a Group 15 metal; each X is a halogen; andy is 3,4 or
 5. 40. The process of claim 1, wherein the catalyst systemcomprises one or more Lewis acid(s) represented by the formulaMR_(n)X_(y-n); wherein M is a Group 15 metal; each R is a monovalent C₁to C₁₂ hydrocarbon radical independently selected from the groupconsisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkylradicals; n is an integer from 0 to 4; y is 3, 4 or 5, wherein n is lessthan y; and each X is a halogen.
 41. The process of claim 1, wherein thecatalyst system comprises one or more Lewis acid(s) represented by theformula M(RO)_(n)R′_(m)X_(y-(m+n)); wherein M is a Group 15 metal, eachRO is a monovalent C₁ to C₃₀ hydrocarboxy radical independently selectedfrom the group consisting of an alkoxy, aryloxy, arylalkoxy,alkylaryloxy radicals; each R′ is a monovalent C₁ to C₁₂ hydrocarbonradical independently selected from the group consisting of an alkyl,aryl, arylalkyl, alkylaryl and cycloalkyl radicals; n is an integer from0 to 4; m is an integer from 0 to 4; y is 3, 4 or 5, wherein the sum ofn and m is less than y; and each X is a halogen.
 42. The process ofclaim 1, wherein the catalyst system comprises one or more Lewis acid(s)represented by the formula M(RC═OO)_(n)R′_(m)X_(y-(m+n)); wherein M is aGroup 15 metal; each RC═OO is a monovalent C₂ to C₃₀ hydrocarbacyloxyradical independently selected from the group consisting of analkacyloxy, arylacyloxy, arylalkylacyloxy, alkylarylacyloxy radicals;each R′ is a monovalent C₁ to C₁₂ hydrocarbon radical independentlyselected from the group consisting of an alkyl, aryl, arylalkyl,alkylaryl and cycloalkyl radicals; n is an integer from 0 to 4; m is aninteger from 0 to 4; y is 3, 4 or 5, wherein the sum of n and m is lessthan y; and each X is a halogen.
 43. The process of claim 1, wherein thecatalyst system comprises one or more Lewis acid(s) independentlyselected from the group consisting of titanium tetrachloride, titaniumtetrabromide, vanadium tetrachloride, tin tetrachloride, zirconiumtetrachloride, titanium bromide trichloride, titanium dibromidedichloride, vanadium bromide trichloride, tin chloride trifluoride,benzyltitanium trichloride, dibenzyltitanium dichloride, benzylzirconiumtrichloride, dibenzylzirconium dibromide, methyltitanium trichloride,dimethyltitanium difluoride, dimethyltin dichloride, phenylvanadiumtrichloride, methoxytitanium trichloride, n-butoxytitanium trichloride,di(isopropoxy)titanium dichloride, phenoxytitanium tribromide,phenylmethoxyzirconium trifluoride, methyl methoxytitanium dichloride,methyl methoxytin dichloride, benzyl isopropoxyvanadium dichloride,acetoxytitanium trichloride, benzoylzirconium tribromide,benzoyloxytitanium trifluoride, isopropoyloxytin trichloride, methylacetoxytitanium dichloride, benzyl benzoyloxyvanadium chloride, vanadiumoxytrichloride, aluminum trichloride, boron trifluoride, galliumtrichloride, indium trifluoride, ethylaluminum dichloride,methylaluminum dichloride, benzylaluminum dichloride, isobutylgalliumdichloride, diethylaluminum chloride, dimethylaluminum chloride,ethylaluminum sesquichloride, methylaluminum sesquichloride,trimethylaluminum, triethylaluminum, methoxyaluminum dichloride,ethoxyaluminum dichloride, 2,6-di-tert-butylphenoxyaluminum dichloride,methoxy methylaluminum chloride, 2,6-di-tert-butylphenoxy methylaluminumchloride, isopropoxygallium dichloride, phenoxy methylindium fluoride,acetoxyaluminum dichloride, benzoyloxyaluminum dibromide,benzoyloxygallium difluoride, methyl acetoxyaluminum chloride,isopropoyloxyindium trichloride, antimony hexachloride, antimonyhexafluoride, arsenic pentafluoride, antimony chloride pentafluoride,arsenic trifluoride, bismuth trichloride arsenic fluoride tetrachloride,tetraphenylantimony chloride, triphenylantimony dichloride,tetrachloromethoxyantimony, dimethoxytrichloroantimony,dichloromethoxyarsine, chlorodimethoxyarsine, difluoromethoxyarsine,acetatotetrachloroantimony, (benzoato) tetrachloroantimony, and bismuthacetate chloride.
 44. The process of claim 1, wherein the catalystsystem comprises one or more Lewis acid(s) independently selected fromthe group consisting of aluminum trichloride, aluminum tribromide,ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminumchloride, methylaluminum dichloride, methylaluminum sesquichloride,dimethylaluminum chloride, boron trifluoride, and titaniumtetrachloride.
 45. The process of claim 1, wherein the catalyst systemcomprises a Lewis acid that is not a compound represented by formulaMX₃, where M is a group 13 metal, X is a halogen.
 46. The process ofclaim 1, wherein the catalyst system comprises a hydrogen halide, acarboxylic acid, a carboxylic acid halide, a sulfonic acid, an alcohol,a phenol, a polymeric halide, a tertiary alkyl halide, a tertiaryaralkyl halide, a tertiary alkyl ester, a tertiary aralkyl ester, atertiary alkyl ether, a tertiary aralkyl ether, an alkyl halide, an arylhalide, an alkylaryl halide or an arylalkylacid halide.
 47. The processof claim 1, wherein the catalyst system comprises one or moreinitiator(s) independently selected from the group consisting of HCl,H₂O, methanol, (CH₃)₃CCl, C₆H₅C(CH₃)₂Cl,(2-Chloro-2,4,4-trimethylpentane) and 2-chloro-2-methylpropane.
 48. Theprocess of claim 1, wherein the catalyst system comprises one or moreinitiator(s) independently selected from the group consisting ofhydrogen chloride, hydrogen bromide, hydrogen iodide, acetic acid,propanoic acid, butanoic acid; cinnamic acid, benzoic acid,1-chloroacetic acid, dichloroacetic acid, trichloroacetic acid,trifluoroacetic acid, p-chlorobenzoic acid, p-fluorobenzoic acid, acetylchloride, acetyl bromide, cinnamyl chloride, benzoyl chloride, benzoylbromide, trichloroacetylchloride, trifluoroacetylchloride,p-fluorobenzoylchloride, methanesulfonic acid, trifluoromethanesulfonicacid, trichloromethanesulfonic acid, p-toluenesulfonic acid,methanesulfonyl chloride, methanesulfonyl bromide,trichloromethanesulfonyl chloride, trifluoromethanesulfonyl chloride,p-toluenesulfonyl chloride, methanol, ethanol, propanol, 2-propanol,2-methylpropan-2-ol, cyclohexanol, benzyl alcohol, phenol,2-methylphenol, 2,6-dimethylphenol, p-chlorophenol, p-fluorophenol,2,3,4,5,6-pentafluorophenol, and 2-hydroxynaphthalene.
 49. The processof claim 1, wherein the catalyst system comprises one or moreinitiator(s) independently selected from the group consisting of2-chloro-2,4,4-trimethylpentane; 2-bromo-2,4,4-trimethylpentane;2-chloro-2-methylpropane; 2-bromo-2-methylpropane;2-chloro-2,4,4,6,6-pentamethylheptane;2-bromo-2,4,4,6,6-pentamethylheptane; 1-chloro-1-methylethylbenzene;1-chloroadamantane; 1-chloroethylbenzene;1,4-bis(1-chloro-1-methylethyl)benzene;5-tert-butyl-1,3-bis(1-chloro-1-methylethyl)benzene;2-acetoxy-2,4,4-trimethylpentane; 2-benzoyloxy-2,4,4-trimethylpentane;2-acetoxy-2-methylpropane; 2-benzoyloxy-2-methylpropane;2-acetoxy-2,4,4,6,6-pentamethylheptane;2-benzoyl-2,4,4,6,6-pentamethylheptane; 1-acetoxy-1-methylethylbenzene;1-aceotxyadamantane; 1-benzoyloxyethylbenzene;1,4-bis(1-acetoxy-1-methylethyl)benzene;5-tert-butyl-1,3-bis(1-acetoxy-1-methylethyl)benzene;2-methoxy-2,4,4-trimethylpentane; 2-isopropoxy-2,4,4-trimethylpentane;2-methoxy-2-methylpropane; 2-benzyloxy-2-methylpropane;2-methoxy-2,4,4,6,6-pentamethylheptane;2-isopropoxy-2,4,4,6,6-pentamethylheptane;1-methoxy-1-methylethylbenzene; 1-methoxyadamantane;1-methoxyethylbenzene; 1,4-bis(1-methoxy-1-methylethyl)benzene;5-tert-butyl-1,3-bis(1-methoxy-1-methylethyl)benzene, and1,3,5-tris(1-chloro-1-methylethyl)benzene.
 50. The process of claim 1,wherein the catalyst system comprises a weakly-coordinating anion. 51.The process of claim 1, wherein the catalyst system comprises one ormore initiator(s) comprising greater than 30 ppm water (based uponweight).
 52. The process of claim 1, wherein the one or more monomer(s)is independently selected from the group consisting of olefins,alpha-olefins, disubstituted olefins, isoolefins, conjugated dienes,non-conjugated dienes, styrenics, substituted styrenics, and vinylethers.
 53. The process of claim 1, wherein the one or more monomer(s)is independently selected from the group consisting of isobutylene,styrene, para-alkylstyrene, para-methylstyrene, alpha-methyl styrene,divinylbenzene, diisopropenylbenzene, isobutylene, 2-methyl-1-butene,3-methyl-1-butene, 2-methyl-2-pentene, isoprene, butadiene,2,3-dimethyl-1,3-butadiene, β-pinene, myrcene, 6,6-dimethyl-fulvene,hexadiene, cyclopentadiene, methyl cyclopentadiene, piperylene, methylvinyl ether, ethyl vinyl ether, and isobutyl vinyl ether.
 54. Theprocess of claim 1, wherein the one or more monomer(s) comprise at least80 wt % isobutylene based upon the total weight of the one or moremonomer(s).
 55. The process of claim 1, wherein the polymerizationtemperature is from 15° C. to −100° C.
 56. The process of claim 1,wherein the polymerization temperature is from −30° C. to −70° C. 57.The process of claim 1, wherein the polymerization temperature is from−40° C. to −60° C.
 58. (canceled)
 59. (canceled)